# Patent

## Title
Glass frit

## Abstract

A glass frit having a low melting point containing (A) Ag2O, (B) V2O5, and (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO and P2O5. The glass frit preferably contains 40 to 70% by mass of (A), 10 to 40% by mass of (B), and 0.5 to 30% by mass of (C) with respect to the total mass in terms of oxides. Furthermore, the glass frit preferably has a mass ratio (Ag2O/V2O5) of (A) to (B) of 1.8 to 3.2.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is the United States national application under 35 USC 371 of International application Serial No. PCT/JP 2014/051854 filed on Jan. 1, 2013, which claims the benefit under 35 USC 119(e) of U.S. provisional application Ser. No. 61/759,630 filed on Feb. 1, 2013.


TECHNICAL FIELD
The present invention relates to a glass frit having a low melting point and not containing toxic substances such as lead, arsenic, antimony, and tellurium.
BACKGROUND ART
Glass frit is used in die attach materials for bonding a semiconductor device such as a silicon carbide (SiC) chip to a substrate or for electrically conductive pastes for forming electrodes. Furthermore, glass frit is used in sealing materials for electronic components, such as ceramic packages for housing integrated circuit devices, and display devices. Considering the properties of adherends that are significantly sensitive to heat, die attach materials, electrically conductive pastes, or sealing materials that exhibit adhesion at relatively low temperatures have been demanded. For such a die attach material, electrically conductive paste, or sealing material that exhibits adhesion at relatively low temperatures, a composition containing a low-melting-point glass is used.
PbO—B2O3-based low-melting-point glasses have been conventionally known as low-melting-point glasses. Patent Document 1 discloses, as a glass having a low softening point, a glass containing: 20 to 70% silver oxide, 10 to 70% of an oxide of vanadium or molybdenum, and 10 to 70% of an oxide of metalloid selected from the group consisting of phosphorus, germanium, arsenic, antimony, bismuth, and tellurium (Patent Document 1).
Patent Document 2 discloses, as a glass that can be sintered at a lower temperature than that for conventional PbO—B2O3-based low-melting-point glasses, a low-melting-point glass containing: 8 to 20% Ag2O, 20 to 35% MoO3, 1 to 6% ZnO, 30 to 55% TeO2, and 5 to 19% V2O5 (Patent Document 2).
Furthermore, as a glass used in die attach materials and the like, for example, a glass that forms a Ag2O—V2O5—TeO2—PbO2 crystal, where the glass contains: approximately 40 to 65% Ag2O, approximately 15 to 35% V2O5, approximately 0 to 50% of at least one oxide selected from the group consisting of TeO2, PbO2, and Pb3O4, in terms of mass ratio based on oxides, has been disclosed (e.g., Patent Document 3). The glass disclosed in Patent Document 3 is, for example, used in a paste for adhering a temperature sensitive device at a low temperature (e.g., 350° C.) in a ceramic package for housing a temperature sensitive integrated circuit device.
PRIOR ART DOCUMENTS
Patent Document
Patent Document 1: Japanese Unexamined Patent Publication No. Sho 51-138711
Patent Document 2: Japanese Unexamined Patent Publication No. Hei 08-259262 (unexamined, published Japanese patent application)
Patent Document 3: Japanese Patent Kohyo Publication No. Hei 08-502468
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
However, PbO—B2O3-based low-melting-point glasses and the low-melting-point glasses disclosed in Patent Documents 1 to 3 often contain toxic substances such as lead (Pb), arsenic (As), antimony (Sb), and tellurium (Te). Due to the growing concerns on the environment in recent years, use of a glass that is free of toxic substances in die attach materials, electrically conductive pastes, or sealing materials has been desired. Furthermore, for die attach materials, electrically conductive pastes, or sealing materials, use of a low-melting-point glass that can be applied to semiconductor devices or integrated circuit devices that are extremely sensitive to heat has been desired.
In response to the circumstances described above, an object of the present invention is to provide a glass frit having a low melting point and not containing toxic substances such as lead, arsenic, antimony, and tellurium.
Means for Solving the Problems
The present invention 1 relates to a glass frit comprising: (A) Ag2O, (B) V2O5, and (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5.
The present invention 2 relates to the glass frit of the present invention 1, further comprising (D) at least one second oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3.
The present invention 3 relates to the glass frit of the present invention 1, where component (C) is MoO3 and ZnO, MoO3 and CuO, or ZnO and CuO.
The present invention 4 relates to the glass frit of the present invention 1, where component (C) is MoO3, ZnO, and CuO.
The present invention 5 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5.
The present invention 6 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) two first oxides selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5.
The present invention 7 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5, and (D) at least one second oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3.
The present invention 8 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) MoO3.
The present invention 9 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) MoO3 and ZnO.
The present invention 10 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) MoO3 and CuO.
The present invention 11 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) ZnO and CuO.
The present invention 12 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, and (C) MoO3, ZnO, and CuO.
The present invention 13 relates to a glass frit essentially consisting of: (A) Ag2O, (B) V2O5, (C) MoO3, and (D) at least one oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3.
The present invention 14 relates to the glass frit of any of the present inventions 1 to 13, where the component (A) content is 40 to 70% by mass, the component (B) content is 10 to 40% by mass, and the component (C) content is 0.5 to 30% by mass, with respect to the total mass in terms of oxides.
The present invention 15 relates to the glass frit of the present invention 14, where the content of a first oxide selected from MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, or P2O5 in component (C) is 0.5 to 15% by mass, with respect to the total mass in terms of oxides.
The present invention 16 relates to the glass frit of any of the present inventions 1 to 15, where the mass ratio of component (A) to component (B) (Ag2O/V2O5) is 1.8 to 3.2.
The present invention 17 relates to the glass frit of any of the present inventions 2 and 13 to 16, where the component (D) content is 0 to 15% by mass with respect to the total mass in terms of oxides.
The present invention 18 relates to the glass frit of any of the present inventions 9 and 14 to 17, where the mass ratio (MoO3:ZnO) of MoO3 to ZnO in component (C) is 12:1 to 1:12.
The present invention 19 relates to the glass frit of any of the present inventions 10 and 14 to 17, where the mass ratio (MoO3:CuO) of MoO3 to CuO in component (C) is 12:1 to 1:10.
The present invention 20 relates to the glass frit of any of the present inventions 11 and 14 to 17, where the mass ratio (ZnO:CuO) of ZnO to CuO in component (C) is 12:1 to 1:12.
The present invention 21 relates to the glass frit of any of the present inventions 12 and 14 to 17, where the mass ratio (MoO3:total amount of ZnO and CuO) of MoO3 to the total amount of ZnO and CuO in component (C) is 12:1 to 1:12.
Effect of the Invention
The present invention can provide a glass frit having a low melting point and not containing toxic substances such as lead (Pb), arsenic (As), antimony (Sb), and tellurium (Te). The glass frit having a low melting point of the present invention has, for example, a glass transition temperature (Tg) of 300° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 500° C. or lower. The glass frit of the present invention can be used in die attach materials, electrically conductive pastes, or sealing materials.


MODE FOR CARRYING OUT THE INVENTION
Glass Frit
The present invention relates to a glass frit containing: (A) Ag2O, (B) V2O5, and (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5.
The glass frit preferably has properties described below.
(1) The glass transition temperature (Tg) of the glass frit is preferably 300° C. or lower, more preferably 250° C. or lower, even more preferably 200° C. or lower, and particularly preferably 180° C. or lower. The lower the glass transition temperature (Tg) of the glass frit is, the lower the treatment temperature can be. On the other hand, the glass transition temperature (Tg) of the glass frit is preferably 80° C. or higher so that high thermal stress resistance properties of the glass can be maintained.
(2) The crystallization temperature (Tc) of the glass frit is preferably 400° C. or lower, more preferably 380° C. or lower, even more preferably 350° C. or lower, and particularly preferably 300° C. or lower. The lower the crystallization temperature (Tc) of the glass frit is, the lower the treatment temperature can be. On the other hand, the crystallization temperature (Tc) of the glass frit is preferably 100° C. or higher so that high thermal stress resistance properties of the glass can be maintained.
(3) The crystal-remelting temperature (Tr) of the glass frit is preferably 500° C. or lower, more preferably 480° C. or lower, even more preferably 450° C. or lower, and particularly preferably 400° C. or lower. The lower the crystal-remelting temperature (Tr) of the glass frit is, the lower the treatment temperature can be. On the other hand, the crystal-remelting temperature (Tr) of the glass frit is preferably 200° C. or higher so that high thermal stress resistance properties of the glass can be maintained.
The glass frit preferably has a glass transition temperature (Tg) of 300° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 500° C. or lower. The glass frit of the present invention can be used in, for example, die attach materials, electrically conductive pastes, or sealing materials. Examples of the electrically conductive paste include electrically conductive pastes for forming electrodes. The die attach material or the electrically conductive paste is required to have electrical conductivity or thermal conductivity. The sealing material is not required to have electrical conductivity or thermal conductivity.
A die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can bond an adherend by sufficiently wetting and spreading over the adhesive interface since the fluidity thereof is enhanced at relatively low treatment temperatures (e.g., 500° C. or lower). Furthermore, the glass frit of the present invention allows crystallization to proceed adequately without causing excessive crystallization since the glass frit recrystallizes at relatively low temperatures of 350° C. or lower, thereby bringing the state of the crystals closer to a eutectic state. Furthermore, the glass frit of the present invention has a crystal-remelting temperature (Tr) of 500° C. or lower. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can inhibit cracking or the like that is caused by inconsistency in expansion rates between an adherend and a crystallized glass structure when, after the adherend has been bonded, the device is placed under conditions where electronic components or the like containing the adherend are subjected to thermal cycles. The die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can exhibit high thermal stress resistance and maintain high adhesion. The glass frit of the present invention can be used in die attach materials, electrically conductive pastes, or sealing materials that can be applied to adherends that are extremely sensitive to heat. Examples of adherends that are extremely sensitive to heat include electronic components, such as display devices and ceramic packages for housing integrated circuit devices, and the like.
Component (C) of the glass frit contains at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5, and may contain two or more first oxides or three or more first oxides.
When the glass frit contains two or more first oxides of component (C), component (C) is preferably MoO3 and ZnO, MoO3 and CuO, or ZnO and CuO.
When the glass frit contains three or more first oxides of component (C), component (C) is preferably MoO3, ZnO, and CuO.
The glass frit of the present invention preferably further contains (D) at least one second oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3. The glass frit of the present invention allows crystallization to proceed adequately without causing excessive crystallization since the contained second oxide, which is component (D), allows formation of crystals that are in a more complicated, eutectic state. The glass frit of the present invention can be used in, for example, die attach materials, electrically conductive pastes, or sealing materials. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can inhibit cracking or the like that is caused by inconsistency in expansion rates between an adherend and a crystallized glass structure when, after the adherend has been bonded, the device is placed under conditions where electronic components or the like containing the adherend are subjected to thermal cycles. The die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can exhibit high thermal stress resistance and maintain high adhesion.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) two first oxides selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, (C) at least one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5, and (D) at least one second oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3.
The glass frit preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) MoO3. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
In the glass frit of the present invention, the composition thereof preferably has a component (A) content of 40 to 70% by mass, a component (B) content of 10 to 40% by mass, and a component (C) content of 0.5 to 30% by mass, with respect to the total mass in terms of oxides. When the composition of each component is within the range described above, the glass frit has a preferable glass transition temperature (Tg: 300° C. or lower, for example), a preferable crystallization temperature (Tc: 400° C. or lower, for example), and a preferable crystal-remelting temperature (Tr: 500° C. or lower, for example). The glass frit can be used in, for example, die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can enhance fluidity at relatively low treatment temperatures (e.g., 500° C. or lower). Furthermore, a die attach material, electrically conductive paste, or sealing material containing the glass frit can bond an adherend at relatively low temperatures (e.g., 500° C. or lower).
Furthermore, the glass frit of the present invention does not excessively crystallize since the glass frit recrystallizes at relatively low temperatures (e.g., 400° C. or lower) and approaches a eutectic state. A die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can exhibit high thermal stress resistance and maintain high adhesion after being bonded to an adherend. In the glass frit of the present invention, when the composition of each component is out of the range described above, adhesion or the like may be affected since melting of the glass frit in lower temperature ranges (e.g., 450° C. or lower) becomes difficult.
In the present description, the composition of each component contained in the glass frit is expressed in % by mass with respect to the total mass of the glass frit in terms of oxide, unless otherwise specified.
In the glass frit of the present invention, the composition thereof more preferably has a component (A) content of 50 to 70% by mass, a component (B) content of 10 to 35% by mass, and a component (C) content of 0.5 to 20% by mass, with respect to the total mass in terms of oxides.
Furthermore, in the glass frit of the present invention, the composition thereof more preferably has a component (A) content of 52 to 70% by mass, a component (B) content of 10 to 33% by mass, and a component (C) content of 0.5 to 15% by mass, with respect to the total mass in terms of oxides.
When the glass frit of the present invention contains two or more substances in component (C), the content of a substance selected from MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, or P2O5 is preferably 0.5 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass.
In the glass frit of the present invention, the component (D) content is preferably 0 to 15% by mass, more preferably 0.5 to 12% by mass, and even more preferably 0.5 to 10% by mass, with respect to the total mass in terms of oxides.
In the glass frit of the present invention, the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6. When the mass ratio (Ag2O/V2O5) of component (A) to component (B) is within the range described above, the glass frit has a preferable glass transition temperature (Tg: 300° C. or lower, for example), a preferable crystallization temperature (Tc: 400° C. or lower, for example), and a preferable crystal-remelting temperature (Tr: 500° C. or lower, for example). The glass frit of the present invention can be used in, for example, die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can bond an adherend since the fluidity thereof is enhanced at relatively low treatment temperatures (e.g., 500° C. or lower). Furthermore, the glass frit of the present invention does not excessively crystallize since the glass frit recrystallizes at relatively low temperatures (e.g., at 400° C. or lower) and approaches a eutectic state. A die attach material, electrically conductive paste, or sealing material containing the glass frit of the present invention can exhibit high thermal stress resistance and maintain high adhesion after being bonded to an adherend. In the glass frit of the present invention, when the mass ratio (Ag2O/V2O5) of component (A) to component (B) is out of the range described above, adhesion or the like may be affected since melting of the glass frit in lower temperature ranges (e.g., 450° C. or lower) becomes difficult.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) MoO3. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 32% by mass.
(C) The MoO3 content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, yet even more preferably 0.5 to 12% by mass, and particularly preferably 0.5 to 10% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The glass frit preferably essentially consists of: (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, and (C) 0.5 to 30% by mass of MoO3, and the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2.
The glass frit preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) ZnO. The glass frit can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 32% by mass.
(C) The ZnO content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, and yet even more preferably 0.5 to 10% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The glass frit preferably essentially consists of: (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, and (C) 0.5 to 30% by mass of ZnO, and the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2.
The glass frit preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) CuO. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 32% by mass.
(C) The CuO content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, and yet even more preferably 1 to 15% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The glass frit preferably essentially consists of: (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, and (C) 0.5 to 30% by mass of CuO, and the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) MoO3 and ZnO. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 32% by mass.
(C-1) The MoO3 content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, yet even more preferably 0.5 to 12% by mass, and particularly preferably 0.5 to 10% by mass.
(C-2) The ZnO content is preferably 0.5 to 15% by mass, more preferably 0.5 to 12% by mass, and even more preferably 0.5 to 10% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The mass ratio (MoO3:ZnO) of MoO3 to ZnO in component (C) is preferably 12:1 to 1:12, more preferably 10:1 to 1:10, and particularly preferably 8:1 to 1:8.
The glass frit preferably essentially consists of (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, (C-1) 0.5 to 30% by mass of MoO3, and (C-2) 0.5 to 15% by mass of ZnO, the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, and the mass ratio (MoO3:ZnO) of MoO3 to ZnO in component (C) is preferably 12:1 to 1:12.
More particularly, the glass frit preferably has the following composition.
(A) The Ag2O content is preferably 52 to 65% by mass.
(B) The V2O5 content is preferably 15 to 30% by mass.
(C-1) The MoO3 content is preferably 0.5 to 12% by mass.
(C-2) The ZnO content is preferably 0.5 to 12% by mass.
The glass frit preferably essentially consists of: (A) 52 to 65% by mass of Ag2O, (B) 15 to 30% by mass of V2O5, (C-1) 0.5 to 12% by mass of MoO3, and (C-2) 0.5 to 12% by mass of ZnO.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) MoO3 and CuO. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 32% by mass.
(C-1) The MoO3 content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, yet even more preferably 0.5 to 12% by mass, and particularly preferably 0.5 to 10% by mass.
(C-2) The CuO content is preferably 0.5 to 15% by mass, more preferably 0.5 to 12% by mass, and even more preferably 0.5 to 10% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The mass ratio (MoO3:CuO) of MoO3 to CuO in component (C) is preferably 12:1 to 1:10, more preferably 10:1 to 1:5, and particularly preferably 8:1 to 1:4.
The glass frit preferably essentially consists of (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, (C-1) 0.5 to 30% by mass of MoO3, and (C-2) 0.5 to 15% by mass of CuO, the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, and the mass ratio (MoO3:CuO) of MoO3 to CuO in component (C) is preferably 12:1 to 1:10.
More particularly, the glass frit preferably has the following composition.
(A) The Ag2O content is preferably 55 to 65% by mass.
(B) The V2O5 content is preferably 25 to 30% by mass.
(C-1) The MoO3 content is preferably 0.5 to 12% by mass.
(C-2) The CuO content is preferably 0.5 to 12% by mass.
The glass frit preferably essentially consists of: (A) 55 to 65% by mass of Ag2O, (B) 25 to 30% by mass of V2O5, (C-1) 0.5 to 12% by mass of MoO3, and (C-2) 0.5 to 12% by mass of CuO.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) ZnO and CuO. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance in thermal cycles after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 30% by mass.
(C-1) The ZnO content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, yet even more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 8% by mass.
(C-2) The CuO content is preferably 0.5 to 15% by mass, more preferably 0.5 to 12% by mass, and even more preferably 0.5 to 10% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The mass ratio (ZnO:CuO) of ZnO to CuO in component (C) is preferably 12:1 to 1:12, more preferably 10:1 to 1:10, and particularly preferably 5:1 to 1:5.
The glass frit preferably essentially consists of (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, (C-1) 0.5 to 30% by mass of ZnO, and (C-2) 0.5 to 15% by mass of CuO, the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, and the mass ratio (ZnO:CuO) of ZnO to CuO in component (C) is preferably 12:1 to 1:12.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 55 to 65% by mass.
(B) The V2O5 content is preferably 25 to 30% by mass.
(C-1) The ZnO content is preferably 0.5 to 10% by mass.
(C-2) The CuO content is preferably 0.5 to 10% by mass.
The glass frit preferably essentially consists of: (A) 55 to 65% by mass of Ag2O, (B) 25 to 30% by mass of V2O5, (C-1) 0.5 to 10% by mass of ZnO, and (C-2) 0.5 to 10% by mass of CuO.
The glass frit preferably essentially consists of: (A) Ag2O, (B) V2O5, and (C) MoO3, ZnO, and CuO. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 32% by mass.
(C-1) The MoO3 content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, yet even more preferably 0.5 to 12% by mass, and particularly preferably 0.5 to 10% by mass.
(C-2) The ZnO content is preferably 0.5 to 15% by mass, more preferably 0.5 to 12% by mass, and even more preferably 0.5 to 10% by mass.
(C-3) The CuO content is preferably 0.5 to 15% by mass, more preferably 0.5 to 12% by mass, and even more preferably 0.5 to 10% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The mass ratio (MoO3:total of ZnO and CuO) of MoO3 to the total of ZnO and CuO in component (C) is preferably 12:1 to 1:12, more preferably 10:1 to 1:10, and particularly preferably 8:1 to 1:8. Furthermore, in the total mass of ZnO and CuO, the mass ratio (ZnO:CuO) of ZnO to CuO is preferably 12:1 to 1:12, and more preferably 10:1 to 1:10.
The glass frit preferably essentially consists of: (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, (C-1) 0.5 to 30% by mass of MoO3, (C-2) 0.5 to 15% by mass of ZnO, and (C-3) 0.5 to 15% by mass of CuO, the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, the mass ratio (MoO3:total of ZnO and CuO) of MoO3 to the total of ZnO and CuO in component (C) is preferably 12:1 to 1:12, and, in the total mass of ZnO and CuO, the mass ratio (ZnO:CuO) of ZnO to CuO is 12:1 to 1:12.
More particularly, the glass frit preferably has the following composition.
(A) The Ag2O content is preferably 55 to 65% by mass.
(B) The V2O5 content is preferably 25 to 30% by mass.
(C-1) The MoO3 content is preferably 0.5 to 12% by mass.
(C-2) The ZnO content is preferably 0.5 to 10% by mass.
(C-3) The CuO content is preferably 0.5 to 5% by mass.
The glass frit preferably essentially consists of: (A) 55 to 65% by mass of Ag2O, (B) 25 to 30% by mass of V2O5, (C-1) 0.5 to 12% by mass of MoO3, (C-2) 0.5 to 10% by mass of ZnO, and (C-3) 0.5 to 5% by mass of CuO.
The glass frit of the present invention preferably essentially consists of: (A) Ag2O, (B) V2O5, (C) MoO3, and (D) at least one oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3. A die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, the die attach material, electrically conductive paste, or sealing material containing the glass frit exhibits excellent thermal stress resistance after bonding.
The glass frit preferably has the following composition.
(A) The Ag2O content is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, and even more preferably 50 to 68% by mass.
(B) The V2O5 content is preferably 10 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably 15 to 32% by mass.
(C) The MoO3 content is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, even more preferably 0.5 to 15% by mass, yet even more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 8% by mass.
(D) The content of at least one oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3 is preferably 0 to 15% by mass, more preferably 0.5 to 12% by mass, even more preferably 1 to 10% by mass, and particularly preferably 1 to 8% by mass.
The mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2, more preferably 1.8 to 3.0, even more preferably 1.95 to 2.7, and particularly preferably 1.95 to 2.6.
The glass frit preferably essentially consists of: (A) 40 to 70% by mass of Ag2O, (B) 10 to 40% by mass of V2O5, (C) 0.5 to 30% by mass of MoO3, and (D) 0 to 15% by mass of at least one oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3, and the mass ratio (Ag2O/V2O5) of component (A) to component (B) is preferably 1.8 to 3.2.
The glass frit can be produced by the method described below.
First, as the raw materials of the glass frit, powders of oxides are weighed, mixed, and charged in a crucible. As the raw materials of the glass frit, the crucible, in which the powders of oxides, used as the raw materials, are charged, is placed in a heated oven. The raw materials of the glass frit are heated to the melt temperature of the glass frit (e.g., 700° C.) in the oven, and then maintained at the melt temperature in the oven until the raw materials are fully melted. Thereafter, the crucible containing the melted raw materials of the glass frit is removed from the oven, and the melted raw materials are uniformly stirred. The melted raw materials of the glass frit are then placed on two stainless steel rolls, and the melted raw materials of the glass frit are kneaded by rotating the two rolls using a motor and rapidly cooled at room temperature to form plate glass. Finally, the plate glass can be uniformly dispersed while being crushed in a mortar, and classified using a mesh sieve to obtain a glass frit having a desired particle size. By collecting particles that pass through a 100 mesh sieve but remain on a 200 mesh sieve, a glass frit having an average diameter of 149 μm (median diameter) can be obtained. Note that glass frit sizes are not limited to those described in the Examples, and glass frits having a larger average diameter or a smaller average diameter can be obtained depending on the mesh size of the sieve.
Die Attach Material or Electrically Conductive Paste
The glass frit can be used in die attach materials or electrically conductive pastes required to have electrical conductivity and/or thermal conductivity.
Die attach materials or the electrically conductive pastes contain glass frit, electrically conductive powder, and an organic vehicle. The glass frit in a die attach material or an electrically conductive paste play an important role in reducing contact resistance between a silicon chip (die) and a substrate such as a metal ceramic when, for example, the chip and the substrate are bonded using the die attach material or the electrically conductive paste. A die attach material or electrically conductive paste containing glass frit, electrically conductive powder, and an organic vehicle exhibits excellent adhesion at low temperatures (e.g., 500° C. or lower). Furthermore, a die attach material or electrically conductive paste containing the glass frit of the present invention exhibits excellent thermal stress resistance after bonding.
The electrically conductive powder contained in a die attach material or an electrically conductive paste is preferably silver powder.
The glass frit content of a die attach material or an electrically conductive paste is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the electrically conductive powder.
Die attach materials or electrically conductive pastes contain an organic vehicle. Examples of organic vehicles include organic binders and solvents. Organic binders and solvents have such functions as controlling the viscosity of the die attach material or the electrically conductive paste, and organic binders and solvents are not particularly limited. The organic binder can be also used after being dissolved in a solvent.
The organic binder to be used can be selected from cellulose-based resins (e.g., ethyl cellulose, nitrocellulose, and the like) or (meth)acrylic resins (e.g., polymethyl acrylate, polymethyl methacrylate, and the like). The organic binder content of the die attach material or the electrically conductive paste is typically 0.2 to 30 parts by mass, and preferably 0.4 to 5 parts by mass, per 100 parts by mass of the electrically conductive powder.
As the solvent to be used, one, or two or more solvents can be selected from alcohols (e.g., terpineol, α-terpineol, β-terpineol, and the like) and esters (e.g., hydroxy group-containing esters, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, butyl carbitol acetate, and the like). The solvent content of the die attach material or the electrically conductive paste is typically 0.5 to 30 parts by mass, and preferably 5 to 25 parts by mass, per 100 parts by mass of the electrically conductive powder.
Additives selected from plasticizers, antifoaming agents, dispersing agents, leveling agents, stabilizing agents, adhesion promoting agents, or the like can be further formulated in the electrically conductive paste if necessary. Among these, the plasticizer to be used can be selected from phthalic acid esters, glycolic acid esters, phosphoric acid esters, sebacic acid esters, adipic acid esters, citric acid esters, and the like.
Next, a method for producing a die attach material or an electrically conductive paste is described.
The method for producing a die attach material or an electrically conductive paste includes a step of mixing electrically conductive powder, glass frit, and an organic vehicle. The electrically conductive paste can be produced by adding electrically conductive powder, glass frit, and, optionally, other additives and additive particles to an organic binder and a solvent, and mixing and dispersing the mixture.
The mixing can be performed using, for example, a planetary mixer. Furthermore, the dispersing can be performed using a three-roll mill. The methods of mixing and dispersing are not limited to these methods, and various known methods can be used.
Sealing Material
The glass frit of the present invention can be used in sealing materials for electronic components or the like that are not required to have electrical conductivity or thermal conductivity. The sealing material preferably contains the glass frit of the present invention and inorganic fillers for adjusting the coefficient of linear expansion. The sealing material may be a paste sealing material that further contains an organic vehicle as well as the glass frit. Organic vehicles similar to those used in die attach materials or electrically conductive pastes can be used. As the inorganic fillers for adjusting the coefficient of linear expansion, at least one inorganic filler selected from the group consisting of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, cordierite, eucryptite, spodumene, zirconium phosphate-based compounds, tin oxide-based compounds, and quartz solid solutions can be used.
Sealing materials containing the glass frit of the present invention can be used in sealing processes at low temperatures (e.g., at 500° C. or lower) where thermal effects on adherends are low and thermal energy consumption can be reduced. Sealing materials containing the glass frit of the present invention exhibit excellent thermal stress resistance in thermal cycles also after sealing. Sealing materials containing the glass frit of the present invention can be suitably used as a sealing material for opening parts or joint parts of various electronic components and electric products such as semiconductor devices, semiconductor packages, fluorescent indicator panels, plasma display panels, organic EL display panels, and liquid crystal display panels.
EXAMPLES
The present invention is described below in further detail using Examples and Comparative Examples. However, the present invention is not limited to these Examples.
Examples and Comparative Examples
The glass frit essentially consisting of (A) Ag2O, (B) V2O5, and (C) one first oxide selected from the group consisting of MoO3, ZnO, CuO, TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5 is shown in Tables 1 and 2.
In Table 1, Comparative Example 1 is a glass frit essentially consisting of (A) Ag2O, (B) V2O5, and (C′) TeO2, which is a toxic substance. In Table 1, Comparative Example 2 is a glass frit essentially consisting of (A) Ag2O, (B) V2O5, and (C′′) Sb2O3, which is a toxic substance.
The method for producing glass frits is as described below.
As the raw materials of the glass frit, powders of oxides described in Tables 1 and 2 were weighed, mixed, and charged in a crucible (e.g., porcelain crucible: high temperature porcelain manufactured by Fisher Brand, size: 10 mL). As the raw materials of the glass frit, a crucible, in which the powders of oxides that were the raw materials were charged, was placed in an oven (oven: JEL-BURN JM, manufactured by JELENKO, Model: 335300). The raw materials of the glass frit were heated in the oven to the melt temperature designated as “Melt Temp” in Tables 1 and 2. The raw materials of the glass frit were maintained at the melt temperature in the oven and were fully melted. Thereafter, the crucible containing the melted raw materials of the glass frit was removed from the oven, and the melted raw materials were uniformly stirred. The melted raw materials of the glass frit were then placed on two rotatable stainless steel rolls having a diameter of 1.86 inches, and the melted raw materials of the glass frit were kneaded by rotating the two rolls using a motor (BODUNE. DC MOTOR 115V) and rapidly cooled at room temperature to form plate glass. The plate glass was finally uniformly dispersed while being crushed in a mortar, and classified using a 100 mesh sieve and a 200 mesh sieve to obtain a sieve-classified glass frit having a desired size. By collecting those that passed through the 100 mesh sieve but remained on the 200 mesh sieve, a glass frit having an average diameter of 149 μm (median diameter) was obtained. Glass frits having a larger average diameter or a smaller average diameter can be obtained depending on the mesh size of the sieve.
A DSC curve was measured for each glass frit using a differential scanning calorimeter under the following conditions. The glass transition temperature (Tg), crystallization temperature (Tc), and crystal-remelting temperature (Tr) of the glass frit were measured from the DSC curve obtained by differential scanning calorimetry.
Glass Transition Temperature (Tg)
A DSC curve was measured for the glass frit in a temperature region of approximately 50° C. to approximately 370° C. by raising the temperature to 370° C. at a rate of temperature increase of 25° C./min using a differential scanning calorimeter DSC-50 manufactured by Shimadzu. The first inflection point temperature in the DSC curve was taken as the glass transition temperature (Tg). When no inflection point was observed in the DSC curve, the glass transition temperature (Tg) of the glass frit was deemed unmeasurable, which is indicated as “(-)” in Tables 1 to 3.
Crystallization Temperature (Tc)
In a DSC curve measured under the same conditions as for the glass transition temperature (Tg), the temperature at the top of an exothermic peak was taken as the crystallization temperature (Tc). When multiple exothermic peaks were present, the temperature at the top of a first exothermic peak was taken as TC1, the temperature at the top of a second exothermic peak was taken as TC2, and the temperature at the top of a third exothermic peak was taken as TC3. The amounts of heat generated (J/g) at the top of exothermic peaks are shown in Tables 1 to 13.
Crystal-Remelting Temperature (Tr)
In a DSC curve measured under the same conditions as for the glass transition temperature (Tg), the temperature at the top of an endothermic peak was taken as the crystal-remelting temperature (Tr). When multiple endothermic peaks were present, the temperature at the top of a first endothermic peak was taken as TR1, the temperature at the top of a second endothermic peak was taken as TR2, and the temperature at the top of a third endothermic peak was taken as TR3. The amounts of heat generated (J/g) at the top of endothermic peaks are indicated by negative values in Tables 1 to 13. The glass frit obtained was visually examined, and homogeneous glass frit was evaluated as “Good” and heterogeneous glass frit was evaluated as “Bad”. The results are shown in Tables 1 and 2.
















TABLE 1









Comparative
Comparative










example 1
example 2
Example 1
Example 2
Example 3
Example 4
Example 5
Example 6



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200





(A)
Ag2O: 231.7 g/mol
65.81
60.67
63.40
61.70
65.60
63.07
65.50
63.07


(B)
V2O5: 181.9 g/mol
30.19
27.83
29.10
28.30
30.10
28.93
30.10
28.93


(C)
MoO3: 143.9 g/mol

7.50
7.5
10.00







ZnO: 81.4 g/mol






4.39
8.00



CuO: 79.5 g/mol




4.30
8.00





TiO2: 79.9 g/mol











Bi2O3: 466.0 g/mol











MnO2: 86.9 g/mol











MgO: 102 g/mol











Nb2O5: 265.8 g/mol











BaO: 153.3 g/mol











P2O5: 141.94 g/mol










(D)
SiO2: 60.1 g/mol











Al2O3: 102 g/mol











SnO: 134.7 g/mol











Fe2O3: 159.7 g/mol











WO3 231.8 g/mol










(C′)
TeO2 159.6 g/mol
4.00









(C′′)
Sb2O3 291.5 g/mol

4.00









Total
100.00
100.00
100.0
100.00
100.00
100.00
99.99
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
600
700
700
700
700



Tg (C.)
125.96
161.39
147.16
152.84
142.75
157.62
133.92
136.5



(mW)










TC
TC1 − Tg
37.49
22
25.88
26.13
47.32
55.67
56.16
46.29



TC1 (C.)
163.45
183.39
173.04
178.97
190.07
213.49
190.08
182.79



(J/g)
36.4
21
31.13
31.12
20.4
31.16
40.02
18.31



TC2 (C.)
255.98
304.02


221.41

261.74
256.8



(J/g)
4.04
4.18


13.41

3.6
15.31



TC3 (C.)











(J/g)










TR
TR1 (C.)
304.99
—
351.23
361.92
370.27
370.57
366.44
372.17



(J/g)
−16.53
—
−49.43
−27.56
−60.09
−46.42
−62.45
−47.06
















TR2 (C.)
359.11























(J/g)
−46.21










TR3 (C.)











(J/g)











bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good
Good






















Example 7
Example 8
Example 9
Example 10
Example 11
Example 12
Example 13




mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200






(A)
Ag2O: 231.7 g/mol
66.50
54.29
65.34
67.02
59.61
63.07
65.20



(B)
V2O5: 181.9 g/mol
30.50
24.92
29.99
30.76
27.36
28.93
29.80



(C)
MoO3: 143.9 g/mol











ZnO: 81.4 g/mol











CuO: 79.5 g/mol











TiO2: 79.9 g/mol
3.00










Bi2O3: 466.0 g/mol

20.80









MnO2: 86.9 g/mol


4.67








MgO: 102 g/mol



2.22







Nb2O5: 265.8 g/mol




13.03






BaO: 153.3 g/mol





8.00





P2O5: 141.94 g/mol






5.00



(D)
SiO2: 60.1 g/mol











Al2O3: 102 g/mol











SnO: 134.7 g/mol











Fe2O3: 159.7 g/mol











WO3 231.8 g/mol










(C′)
TeO2 159.6 g/mol










(C′′)
Sb2O3 291.5 g/mol











Total
100.00
100.01
100.00
100.00
100.00
100.00
100.00




Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18




Melt Temp (C.)
600
700
700
700
700
700
700




Tg (C.)
—
217.8
140.2
153.26
151.37
153.72
151.37




(mW)










TC
TC1 − Tg
—
—
49.78
46.14
48.06
56.42
36.23




TC1 (C.)
158
—
189.98
199.4
199.43
210.14
187.6




(J/g)
2.8
—
28.96
28.72
29.37
27.68
37.92




TC2 (C.)
250
—
249.97
340.2
266.12
311.46
269.88




(J/g)
0.63
—
6.4
7.54
17.97
9.39
26.4




TC3 (C.)











(J/g)










TR
TR1 (C.)
359
362.4
384.01
372.4
370.9
379
382.31




(J/g)
−1.63
−16.87
−72.24
−5.27
−32.36
−47.79
−1.87




TR2 (C.)
374


382.79


410




(J/g)
−68


−14.3


−83.39




TR3 (C.)











(J/g)











bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g




Melt pour
Good
Good
Good
Good
Good
Good
Good































Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-




ple 78
ple 79
ple 80
ple 81
ple 82
ple 83
ple 84
ple 85
ple 86



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200

























(A)
Ag2O: 231.7 g/mol
68.21
65.81
68.21
65.81
61.70
68.21
65.81
61.70
58.27


(B)
V2O5: 181.9 g/mol
31.29
30.19
31.29
30.19
28.30
31.29
30.19
28.30
26.73


(C)
MoO3: 143.9 g/mol
0.50
4.00










ZnO: 81.4 g/mol


0.50
4.00
10.00







CuO: 79.5 g/mol





0.50
4.00
10.00
15.00



TiO2: 79.9 g/mol












Bi2O3: 466.0 g/mol












MnO2: 86.9 g/mol












MgO: 102 g/mol












Nb2O5: 265.8 g/mol












BaO: 153.3 g/mol












P2O5: 141.94 g/mol











(D)
SiO2: 60.1 g/mol












Al2O3: 102 g/mol












SnO: 134.7 g/mol












Fe2O3: 159.7 g/mol












WO3 231.8 g/mol












TeO2 159.6 g/mol












Sb2O3 291.5 g/mol












Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700
700
700
700



Tg (C.)

134.55
123.24
132.95
140.7
123.39
143.79
151.76
163.77



(mW)











TC
TC1 − Tg

26.17
34.07
56.73
55.56
35
34.37
51.43
54.45



TC1 (C.)
149.09
160.72
157.31
189.68
196.26
158.39
178.16
203.19
218.22



(J/g)
2.2
26.38
14.42
36.59
15.34
9.48
23.06
39.46
15.97



TC2 (C.)

222.63
306.98
267.06
255.25

224.29
295.21




(J/g)

3.09
1.59
2.98
15.19

10.65
1.39




TC3 (C.)

268.54




310.91





(J/g)

3




3.84




TR
TR1 (C.)
372.61
362.02
373.14
364.92
373.3
373.18
370.77
370.47
371.13



(J/g)
−81.43
−65.83
−76.99
−62.39
−40.15
−70.46
−60.36
−47.37
−43.46



TR2 (C.)




420.67







(J/g)




−0.36







TR3 (C.)












(J/g)












bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good
Good
Good









As shown in Tables 1 and 2, the glass frits in these Examples do not contain lead (Pb), arsenic (As), tellurium (Te), or antimony (Sb), which are toxic substances. The glass frits of the Examples have a glass transition temperature (Tg) of 250° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 450° C. or lower. The glass frits of the Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can bond an adherend by sufficiently wetting and spreading over the interface of the adherend since the fluidity thereof at relatively low treatment temperatures (e.g., 450° C. or lower) is enhanced. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can inhibit cracking or the like that is caused by inconsistency in expansion rates between an adherend and a crystallized glass structure when, after being bonded, the device is placed under thermal cycling conditions. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion.
Tables 3 and 4 show glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) one oxide selected from the group consisting of TiO2, Bi2O3, MnO2, MgO, Nb2O5, BaO, and P2O5. The glass frits shown in Tables 3 and 4 were produced by a method similar to Example 1 except that the compositions shown in Tables 3 and 4 were used, and evaluated in a manner similar to Example 1.















TABLE 3









Example 15
Example 16
Example 17
Example 18
Example 20
Example 21
Example 22



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200





(A)
Ag2O: 231.7 g/mol
62.73
62.04
60.67
57.93
62.73
62.04
60.67


(B)
V2O5: 181.9 g/mol
28.77
28.46
27.83
26.57
28.77
28.46
27.83


(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50
7.50
7.50



ZnO: 81.4 g/mol










CuO: 79.5 g/mol










TiO2: 79.9 g/mol




1.00
2.00
4.00



Bi2O3: 466.0 g/mol










MnO2: 66.9 g/mol










MgO: 102 g/mol










Nb2O5: 265.8 g/mol
1.00
2.00
4.00
8.00






BaO: 153.3 g/mol










P2O5: 141.94 g/mol









(D)
SiO2: 60.1 g/mol










Al2O3: 102 g/mol










SnO: 134.7 g/mol










Fe2O3: 159.7 g/mol










WO3 231.8 g/mol










TeO2 159.6 g/mol










Sb2O3 291.5 g/mol










Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.15
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700
700



Tg (C.)
151.47
156.2
164.63
174.88
151.03
151.88
146.91



(mW)









TC
TC1 − Tg
30.08
33.62
58.05
40.95
31.48
29.59
28.09



TC1 (C.)
181.55
189.82
222.68
215.83
182.54
181.47
175



(J/g)
33.71
34.2
35.68
29.72
33.24
32.04
32.33



TC2 (C.)






286.23



(J/g)






3.43



TC3 (C.)










(J/g)










TR1 (C.)
356.6
338.87
358.4
359.21
365.31
365.38
352.87



(J/g)
−42.6
−23.47
30.67
−25.99
−42.52
−39.99
−44.51



TR2 (C.)

396.4
411.03
416.37






(J/g)

−28.65
−21.84
−31.71






TR3 (C.)










(J/g)










bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good




















Example 23
Example 24
Example 25
Example 26
Example 27




mesh
100/200
100/200
100/200
100/200
100/200






(A)
Ag2O: 231.7 g/mol
62.73
62.04
62.04
61.36
60.67



(B)
V2O5: 181.9 g/mol
28.77
28.46
28.46
28.14
27.83



(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50




ZnO: 81.4 g/mol









CuO: 79.5 g/mol









TiO2: 79.9 g/mol









Bi2O3: 466.0 g/mol









MnO2: 66.9 g/mol









MgO: 102 g/mol
1.00
2.00
2.00
3.00
4.00




Nb2O5: 265.8 g/mol









BaO: 153.3 g/mol









P2O5: 141.94 g/mol








(D)
SiO2: 60.1 g/mol









Al2O3: 102 g/mol









SnO: 134.7 g/mol









Fe2O3: 159.7 g/mol









WO3 231.8 g/mol









TeO2 159.6 g/mol









Sb2O3 291.5 g/mol









Total
100.00
100.00
100.00
100.00
100.00




Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18




Melt Temp (C.)
700
700
800
800
800




Tg (C.)
155
161.86
161.48
178.6
190.91




(mW)








TC
TC1 − Tg
47.1
74.97
80.29
89.75
74.54




TC1 (C.)
202.1
236.63
241.75
268.35
265.45




(J/g)
35.58
45.29
42.52
37.7
31.58




TC2 (C.)
341.51
305.08
304.52
300.98
302.63




(J/g)
3.71
1.92
1.86
0.79
0.63




TC3 (C.)









(J/g)









TR1 (C.)
360.87
358.61
358.43
352.43
352.95




(J/g)
−32.35
30.25
−32.79
−31.12
−25.94




TR2 (C.)
416.32
410.01
411.02
400.51
401.27




(J/g)
−5.98
−4.5
−2.76
−5.7
−4.12




TR3 (C.)









(J/g)









bach size
10 g
10 g
10 g
10 g
10 g




Melt pour
Good
Good
Good
Good
Good

























TABLE 4







Example
Example
Example
Example
Example
Example
Example
Example




32
33
34
35
44
45
46
47



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
























(A)
Ag2O: 231.7 g/mol
62.73
62.04
60.67
57.93
62.73
62.04
60.67
57.93


(B)
V2O5: 181.9 g/mol
28.77
28.46
27.83
26.57
28.77
28.46
27.83
26.57


(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50
7.50
7.50
7.50



ZnO: 81.4 g/mol











CuO: 79.5 g/mol











TiO2: 79.9 g/mol











Bi2O3: 466.0 g/mol











MnO2: 86.9 g/mol
1.00
2.00
4.00
8.00







MgO: 102 g/mol











Nb2O5: 265.8 g/mol











BaO: 153.3 g/mol




1.00
2.00
4.00
8.00



P2O5: 141.94 g/mol










(D)
SiO2: 60.1 g/mol











Al2O3: 102 g/mol











SnO: 134.7 g/mol











Fe2O3: 159.7 g/mol











WO3 231.8 g/mol











TeO2 159.6 g/mol











Sb2O3 291.5 g/mol











Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700
700
700



Tg (C.)
163.5
151.11
149.39
173.26
148.19
151.21
151.27
153.39



(mW)










TC
TC1 − Tg
64.84
39.94
35.14
59.98
32.48
38.23
63
62.51



TC1 (C.)
228.34
191.05
184.53
233.24
180.67
189.44
214.27
215.9



(J/g)
38.46
34.62
33.9
38.19
35.61
36.09
34.74
23.1



TC2 (C.)
291.99
304.81

278.79
277.9
262.55
264.18
280.15



(J/g)
8.24
6.46

11.8
7.55
6.44
3
5.27



TC3 (C.)






300.46




(J/g)






2.13




TR1 (C.)
350.14
360.67
350.59
359.42
353.02
355.87
361.35
370.18



(J/g)
−10.62
−23.16
−9.76
−0.77
−48.88
−43.24
−51.52
−70.21



TR2 (C.)
408.43
408.57
370.21
414.75
387.18






(J/g)
−19.14
−17.71
−15.23
−57.55
−5.37






TR3 (C.)











(J/g)











bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good
Good









The glass frits in these Examples containing two substances in component (C) have a glass transition temperature (Tg) of 200° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 450° C. or lower, as shown in Tables 3 and 4. The glass frits of the Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits excellent adhesion at relatively low treatment temperatures, i.e., 450° C. or lower. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion when, after being bonded, the device is placed under thermal cycling conditions.
Tables 5 and 6 show glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) ZnO. The glass frits shown in Tables 5 and 6 were produced by a method similar to Example 1 except that the compositions shown in Tables 5 and 6 were used, and evaluated in a manner similar to Example 1.



















TABLE 5







Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-




ple 36
ple 37
ple 38
ple 39
ple 48
ple 49
ple 50
ple 51
ple 52
ple 53
ple 54



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200



























(A)
Ag2O: 231.7 g/mol
62.73
62.04
60.67
57.93
56.56
55.19
64.44
63.07
58.96
60.33
56.21


(B)
V2O5: 181.9 g/mol
28.77
28.46
27.83
26.57
25.94
25.31
29.56
28.93
27.04
27.67
25.79


(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50
7.50
4.00
4.00
10.00
4.00
10.00



ZnO: 81.4 g/mol
1.00
2.00
4.00
8.00
10.00
12.00
2.00
4.00
4.00
8.00
8.00



CuO: 79.5 g/mol














TiO2: 79.9 g/mol














Bi2O3: 466.0 g/mol














MnO2: 86.9 g/mol














MgO: 102 g/mol














Nb2O5: 26.58 g/mol














BaO: 153.3 g/mol














P2O5: 141.94 g/mol













(D)
SiO2: 60.1 g/mol














Al2O3: 102 g/mol














SnO: 134.7 g/mol














Fe2O3: 159.7 g/mol














WO3 231.8 g/mol














TeO2 159.6 g/mol














Sb2O3 291.5 g/mol














Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700
700
700
700
700
700



Tg (C.)
149.23
150.62
154.03
160.2
159.5
161.63
139.87
144.69
161.12
152.74
167.88



(mW)













TC
TC1 − Tg
32.93
44.84
71.72
80
68.09
62.27
53.06
62.29
73.97
64.16
87.11



TC1 (C.)
182.16
195.46
225.75
240.2
227.59
223.9
192.93
206.98
235.09
216.9
254.99



(J/g)
37.56
38.61
43.22
50.58
36.72
34.59
32.42
42.24
47.74
37.15
51.86



TC2 (C.)


294.36
297.88
256.23
254.12
305.78
303.17

265.45
295.49



(J/g)


2.94
0.96
2.48
3.46
11.77
2.09

3.54
0.91



TC3 (C.)




287.23









(J/g)




0.53








TR
TR1 (C.)
341.45
352.09
342.08
342.74
341.67
341.61
352.7
343.64
341.49
351.75
342.31



(J/g)
−43.54
−37.77
−46.48
−38.36
−31.46
−31.1
−68.62
−66.86
−43.66
−54.15
−78.99



TR2 (C.)


384.15











(J/g)


−15.98











TR3 (C.)














(J/g)














bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good



























TABLE 6







Example
Example
Example
Example
Example
Example
Example
Example
Example
Example




55
56
87
88
89
90
91
92
93
94



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200


























(A)
Ag2O: 231.7 g/mol
54.84
54.84
52.71
59.22
62.48
59.22
62.48
63.78
64.55
54.20


(B)
V2O5: 181.9 g/mol
25.16
25.16
29.29
22.78
19.52
22.78
19.52
18.22
17.45
27.80


(C)
MoO3: 143.9 g/mol
12.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
10.00



ZnO: 81.4 g/mol
8.00
10.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00



CuO: 79.5 g/mol













TiO2: 79.9 g/mol













Bi2O3: 466.0 g/mol













MnO2: 86.9 g/mol













MgO: 102 g/mol













Nb2O5: 265.8 g/mol













BaO: 153.3 g/mol













P2O5: 141.94 g/mol












(D)
SiO2: 60.1 g/mol













Al2O3: 102 g/mol













SnO: 134.7 g/mol













Fe2O3: 159.7 g/mol













WO3 231.8 g/mol












(C′)
TeO2 159.6 g/mol












(C′′)
Sb2O3 291.5 g/mol













Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
1.80
2.60
3.20
2.60
3.20
3.50
3.70
1.95



Melt Temp (C.)
700
700
700
700
700
700
700
700
700
700



Tg (C.)
172.5
172.55
181.2
159.75
145.97
161.15
145.28
—
—
178.12



(mW)












TC
TC1 − Tg
75.21
77.05
70.15
54.44
41.31
54.52
39.54
—
—
76.15



TC1 (C.)
247.71
249.6
251.35
214.19
187.28
215.67
184.82
172.62
191.98
254.27



(J/g)
48.32
43.24
56.01
43.62
12.25
41.78
13.09
1.33

52.33



TC2 (C.)

296.09

313.91
267.61
313.85
262.41
288.41
285.58
296.64



(J/g)

0.6

7.22
3.12
7.49
3.2
11.38
10.03
0.27



TC3 (C.)




290.06

290.39






(J/g)




8.74

8.6





TR
TR1 (C.)
340.27
343.32
340.61
344.55
416.17
344.89
360.98
360.21
360.33
341.05



(J/g)
−9.18
−18.52
−15.98
−32.06
−7.09
−33.99
−19.66
−14.51
−14.05
−38.08



TR2 (C.)
365.31
367.48


460.79

416.67
416.42
416.28




(J/g)
−2.86
−1.46


−18.47

−5.52
−11.04
−12.76




TR3 (C.)
391.02
392.78




459.97
461.24
460.27




(J/g)
−26.93
−10.72




−32.07
−27.33
−24.18




bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good









Table 7 shows glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) CuO. The glass frits shown in Table 7 were produced by a method similar to Example 1 except that the compositions shown in Table 7 were used, and evaluated in a manner similar to Example 1.


















TABLE 7







Example
Example
Example
Example
Example
Example
Example
Example
Example
Example




40
41
42
43
57
58
59
60
61
62



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200
100/200


























(A)
Ag2O: 231.7 g/mol
62.73
62.04
60.67
57.93
56.56
55.19
63.07
60.33
58.96
56.21


(B)
V2O5: 181.93 /mol
28.77
28.46
27.83
26.57
25.94
25.31
28.93
27.67
27.04
25.79


(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50
7.50
4.00
4.00
10.00
10.00



ZnO: 81.4 g/mol













CuO: 79.5 g/mol
1.00
2.00
4.00
8.00
10.00
12.00
4.00
8.00
4.00
8.00



TiO2: 79.9 g/mol













Bi2O3: 466.0 g/mol













MnO2: 86.9 g/mol













MgO: 102 g/mol













Nb2O5: 265.8 g/mol













BaO: 153.3 g/mol













P2O5: 141.94 g/mol












(D)
SiO2: 60.1 g/mol













Al2O3: 102 g/mol













SnO: 134.7 g/mol













Fe2O3: 159.7 g/mol













WO2 231.8 g/mol













TeO2 159.6 g/mol













Sb2O3 291.5 g/mol













Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700
700
700
700
700



Tg (C.)
149.29
152.33
158
172.43
183.48
192.46
151.38
164.95
165.03
178.92



(mW)












TC
TC1 − Tg
33.29
44.46
70.15
57.27
46.72
44.35
70.54
57.67
64.24
53



TC1 (C.)
182.58
196.79
228.15
229.7
230.2
236.81
221.92
222.62
229.27
231.92



(J/g)
36.42
42.29
47.53
43.32
41.26
41.27
40.22
35.13
43.21
46.67



TC2 (C.)

290.65
295.55


329.85

303.81

324.8



(J/g)

2.33
0.49


4.45

2.13

7.95



TC3 (C.)













(J/g)













TR1 (C.)
351.22
358.64
348.37
352.24
346.22
409.64
350.22
348.8
355.99
412.74



(J/g)
−43.45
−37.33
−21.99
−13.67
−5.07
−40.55
−52.54
−52.55
−8.19
−73.51



TR2 (C.)


406.63
406.49
409.16
423.74


408.98




(J/g)


−32.14
−36.61
−67.55
−3.5


−65.79




TR3 (C.)













(J/g)













bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good









Table 8 shows glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) ZnO, and (C-2) CuO. The glass fits shown in Table 8 were produced by a method similar to Example 1 except that the compositions shown in Table 8 were used, and evaluated in a manner similar to Example 1.












TABLE 8







Example
Example
Example
Example




73
74
75
76



mesh
100/200
100/200
100/200
100/200




















(A)
Ag2O: 231.7 g/mol
64.44
63.07
60.33
57.58


(B)
V2O5: 181.9 g/mol
20.56
28.93
27.67
26.42


(C)
MoO3: 143.9 g/mol







ZnO: 81.4 g/mol
2.00
4.00
8.00
8.00



CuO: 79.5 g/mol
4.00
4.00
4.00
8.00



TiO2: 79.9 g/mol







Bi2O3: 466.0 g/mol







MnO2: 86.9 g/mol







MgO: 102 g/mol







Nb2O5: 265.8 g/mol







BaO: 153.3 g/mol







P2O5: 141.94 g/mol






(D)
SiO2: 60.1 g/mol







Al2O3: 102 g/mol







SnO: 134.7 g/mol







Fe2O3: 159.7 g/mol







WO3 231.8 g/mol







TeO2 159.6 g/mol







Sb2O3 291.5 g/mol







Total
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700



Tg (C.)
150.38
151.41
159.48
—



(mW)






TC
TC1 − Tg
43.97
38.06
38.08




TC1 (C.)
194.35
189.47
197.56
215.65



(J/g)
22.68
25.43
18.63
1.49



TC2 (C.)
242.19
225.65
220.06
294.39



(J/g)
11.08
8.61
3.54
2.2



TC3 (C.)
287.92

273.63




(J/g)
1.35

4.22



TR
TR1 (C.)
369.78
367.47
372.99
365.4



(J/g)
−52.73
−50.54
−31.01
−1.34



TR2 (C.)



374.58



(J/g)



−21.15



TR3 (C.)







(J/g)







bach size
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good









As shown in Tables 5 to 8, the glass frits in these Examples containing (A) Ag2O, (B) V2O5, and two substances in component (C) selected from MoO3 and ZnO, MoO3 and CuO, or ZnO and CuO have a glass transition temperature (Tg) of 200° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 465° C. or lower. The glass frits of the Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can bond an adherend at relatively low treatment temperatures, e.g., 465° C. or lower, for example. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion when, after being bonded, the device is placed under thermal cycling conditions.
Table 9 shows glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) ZnO, where the component (A) content is 50 to 65% by mass, the component (B) content is 15 to 30% by mass, the component (C-1) content is 0 to 12% by mass, and the component (C-2) content is 0 to 12% by mass.








TABLE 9








MoO3














0
0.5
4
7.5
10
12


















ZnO
0
melt
—
Example 78
Example 79
Example 1
—
—






(SC300-4)
(SC301-4)
(SC112-4)






Tg

—
135
147




















Tc

149.1
2.2
161
26.4
173
31





Tr

372.6
−66
362
−66
355
−35















Good
Good
Good


















0.5
melt
Example 80
—
—
—
—
—





(SC305-4)









Tg
  123.24





















Tc
157
14.4








Tr
376
−70



















Good





















1
melt
—
—
—
Example 36
—
—








(SC140-4)






Tg



149


















Tc



183
38





Tr



342
−44













Good


















2
melt
—
—
—
Example 37
—
—








(SC141-4)






Tg



151


















Tc



195
39





Tr



352
−38













Good


















4
melt
Example 5
—
Example 51
Example 38
Example 52
—





(SC114-4)

(SC181-4)
(SC142-4)
(SC183-4)





Tg
134

145
154
161




















Tc
190
40

206
42
226
43
235
48




Tr
366
−62

343
−67
342
−46
342
−44















Good

Good
Good
Good

















8
melt
Example 6
—
Example 53
Example 39
Example 54
Example 55





(SC160-4)

(SC182-4)
(SC143-4)
(SC184-4)
(SC223-4)




Tg
137

153
160
168
173




















Tc
183
18

217
37
240
51
254
52
248
48



Tr
372
−47

352
−54
343
−38
342
−79
340
−100














Good

Good
Good
Good
Good
















10
melt
Example 82
—
—
Example 48
Example 56
—





(SC307-4)


(SC176-4)
(SC226-4)





Tg
  140.74


160
173



















Tc
196
15.3


228
37
250
43




Tr
373
−40


342
−31
343
















Good


Good
Good

















12
melt
—
—
—
Example 49
—
—








(SC177-4)






Tg



162


















Tc



224
35





Tr



342
−31













Good











As shown in Table 9, the glass frits essentially consisting of (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) ZnO have a glass transition temperature (Tg) of 180° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 465° C. or lower. The glass frits in these Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can bond an adherend at relatively low treatment temperatures, e.g., 465° C. or lower. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion when, after being bonded, the device is placed under thermal cycling conditions.
Table 10 shows glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) CuO, where the component (A) content is 50 to 65% by mass, the component (B) content is 15 to 30% by mass, the component (C-1) content is 0 to 10% by mass, and the component (C-2) content is 0 to 12% by mass.








TABLE 10








MoO3













0
0.5
4
7.5
10

















CuO
0
melt
—
Example 78
Example 79
Example 1
—






(SC300-4)
(SC301-4)
(SC112-4)





Tg

—
135
147


















Tc

149
2.2
16l
26.4
173
31




Tr

373
−66
362
−66
355
−35













Good
Good
Good
















0.5
melt
Example 83
—
—
—
—





(SC310-4)








Tg
123



















Tc
158
9.48







Tr
376
−70

















Good



















1
melt
—
—
—
Example 40
—








(SC144-4)





Tg



149
















Tc



183
36




Tr



351
−43











Good
















2
melt
—
—
—
Example 41
—








(SC145-4)





Tg



152
















Tc



197
42




Tr



359
−37











Good
















4
melt
Example 84
—
Example 59
Example 42
—





(SC311-4)

(SC185-4)
(SC146-4)





Tg
144

151
158


















Tc
178
23

222
40
228
48




Tr
370
−60

350
−53
348
−22














Good

Good
Good
















8
melt
Example 4
—
Example 60
Example 43
Example 62





(SC159-4)

(SC186-4)
(SC147-4)
(SC188-4)




Tg
158

165
172
179


















Tc
213
31

223
35
230
43
232
47



Tr
371
−46

349
−53
406
−37
413
−73

















Good

Good
Good
Good



10
melt
Example 85
—
—
Example 57
—





(SC312-4)


(SC178-4)





Tg
151


230

















Tc
203
51


230
41




Tr
370
−47


409
−68














Good


Good
















12
melt
—
—
—
Example 58
—








(SC1794)





Tg



192
















Tc



237
41




Tr



410
−41











Good










As shown in Table 10, the glass frits essentially consisting of (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) CuO have a glass transition temperature (Tg) of 200° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 450° C. or lower. The glass frits of these Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can bond an adherend at relatively low treatment temperatures, i.e., 450° C. or lower. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion when, after being bonded, the device is placed under thermal cycling conditions.
Table 10 shows glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C-1) MoO3, (C-2) ZnO, and (C-3) CuO. The glass frits were produced by a method similar to Example 1 except that the compositions shown in Table 11 were used, and evaluated in a manner similar to Example 1.














TABLE 11







Example 68
Example 69
Example 70
Example 71
Example 72
Example 95



mesh
100/200
100/200
100/200
100/200
100/200
100/200






















(A)
Ag2O: 231.7 g/mol
60.67
59.30
59.30
57.93
55.19
53.47


(B)
V2O5: 181.9 g/mol
27.83
27.20
27.20
26.57
25.31
24.53


(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50
10.00



ZnO: 81.4 g/mol
2.00
2.00
4.00
4.00
8.00
8.00



CuO: 79.5 g/mol
2.00
4.00
2.00
4.00
4.00
4.00



TiO2: 79.9 g/mol









Bi2O3: 466.0 g/mol









MnO2: 86.9 g/mol









MgO: 102 g/mol









Nb2O5: 265.8 g/mol









BaO: 153.3 g/mol









P2O5: 141.94 g/mol








(D)
SiO2: 60.1 g/mol









Al2O3: 102 g/mol









SnO: 134.7 g/mol









Fe2O3: 159.7 g/mol









WO3 231.8 g/mol









TeO2 159.6 g/mol









Sb2O3 291.5 g/mol









Total
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700



Tg (C.)
157.81
162.98
164.41
167.4
181.31
190.51



(mW)








TC
TC1 − Tg
67.95
55.02
60.96
52.58
43.58
34.36



TC1 (C.)
225.76
218
225.37
219.98
224.89
224.87



(J/g)
42.76
43.37
41.68
40.71
33.97
30.34



TC2 (C.)
298.82

301.36
321.83
254.53
309.65



(J/g)
1.23

0.7
3.96
1.38
19.27



TC3 (C.)




325.99




(J/g)




3.87



TR
TR1 (C.)
346.83
345
345.18
342.85
341.92
404.58



(J/g)
−32.33
−28.51
−36.83
−27.53
−23.07
−18.57



TR2 (C.)

401.14
395.22
400.09
388.34




(J/g)


−20.98
−21.75
−2.2




TR3 (C.)




418.71




(J/g)




−3.01




bach size
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good









As shown in Table 11, the glass frits of these Examples containing three substances in component (C) have a glass transition temperature (Tg) of 200° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 450° C. or lower. The glass frits of the Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can bond an adherend at relatively low treatment temperatures of 450° C. or lower. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion when, after being bonded, the device is placed under thermal cycling conditions.
Table 12 shows glass frits essentially consisting of: (A) Ag2O, (B) V2O5, (C) MoO3, (D) at least one oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3, and Fe2O3. The glass frits were produced by a method similar to Example 1 except that the compositions shown in Table 12 were used, and evaluated in a manner similar to Example 1.















TABLE 12









Example 14
Example 19
Example 28
Example 29
Example 30
Example 31
Example 63



mesh
100/200
100/200
100/200
100/200
100/200
100/200
100/200





(A)
Ag2O: 231.7 g/mol
62.73
62.73
62.73
62.04
60.67
57.93
64.78


(B)
V2O5: 181.9 g/mol
28.77
28.77
28.77
28.46
27.83
26.57
29.72


(C)
MoO3: 143.9 g/mol
7.50
7.50
7.50
7.50
7.50
7.50
5.00



ZnO: 81.4 g/mol










CuO: 79.5 g/mol










TiO2: 79.9 g/mol










Bi2O3: 466.0 g/mol










MnO2: 86.9 g/mol










MgO: 102 g/mol










Nb2O5: 265.8 g/mol










BaO: 153.3 g/mol










P2O5: 141.94 g/mol









(D)
SiO2: 60.1 g/mol

1.00








Al2O3: 102 g/mol






0.50



SnO: 134.7 g/mol
1.00









Fe2O3: 159.7 g/mol


1.00
2.00
4.00
8.00




WO3 231.8 g/mol










TeO2 159.6 g/mol










Sb2O3 291.5 g/mol










Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Ag2O/V2O5
2.18
2.18
2.18
2.18
2.18
2.18
2.18



Melt Temp (C.)
700
700
700
700
700
700
600



Tg(C.)
149.4
147.17
153.5
158.26
158.86
163.56
141.62



(mW)









TC
TC1 − Tg
23.99
25.96
26.05
51.2
49.98
37.8
27.7



TC1 (C.)
173.39
173.12
179.55
209.46
208.84
201.36
169.32



(J/g)
33.67
31.03
35.38
36.43
37.51
33.95
31.15



TC2 (C.)
289.15


280.71






(J/g)
2.69


1.31






TC3 (C.)










(J/g)









TR
TR1 (C.)
349.34
369.6
374.35
346.01
344.86
367.87
362.14



(J/g)
−36.7
−57.71
−78.97
−56.15
−70.52
−48.84
−52.87



TR2 (C.)





437.48




(J/g)





−10.48




TR3 (C.)










(J/g)










Bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
Good
Good
Good
Good
Good
Good
Good




















Example 64
Example 65
Example 66
Example 67
Example 77




mesh
100/200
100/200
100/200
100/200
100/200






(A)
Ag2O: 231.7 g/mol
63.10
61.40
61.30
60.67
66.44



(B)
V2O5: 181.9 g/mol
28.90
28.10
28.00
27.83
25.56



(C)
MoO3: 143.9 g/mol
7.50
10.00
10.00
7.50
7.5




ZnO: 81.4 g/mol









CuO: 79.5 g/mol









TiO2: 79.9 g/mol









Bi2O3: 466.0 g/mol









MnO2: 86.9 g/mol









MgO: 102 g/mol









Nb2O5: 265.8 g/mol









BaO: 153.3 g/mol









P2O5: 141.94 g/mol








(D)
SiO2: 60.1 g/mol









Al2O3: 102 g/mol
0.50
0.50
1.00

0.5




SnO: 134.7 g/mol









Fe2O3: 159.7 g/mol









WO3 231.8 g/mol



4.00





TeO2 159.6 g/mol









Sb2O3 291.5 g/mol









Total
100.00
100.00
100.00
100.00
100.00




Ag2O/V2O5
2.18
2.19
2.18
2.18
2.60




Melt Temp (C.)
600
600
600
700
600




Tg(C.)
144.04
150.8
156.15
156.08
138.44




(mW)








TC
TC1 − Tg
29.94
29.2
24.8
30.24
46.26




TC1 (C.)
173.98
180
180.95
186.32
184.7




(J/g)
28.74
30.64
30.7
33.46
31.29




TC2 (C.)



309.73
290.43




(J/g)



8.04
4.36




TC3 (C.)









(J/g)








TR
TR1 (C.)
357.04
354.39
362.51
352.56
362.1




(J/g)
−59.78
−19.24
−24.04
−1.93
−55.06




TR2 (C.)



379.7





(J/g)



−29.62





TR3 (C.)









(J/g)









Bach size
10 g
10 g
10 g
10 g
10 g




Melt pour
Good
Good
Good
Good
Good









As shown in Table 12, the glass frits of these Examples containing component (D) have a glass transition temperature (Tg) of 200° C. or lower, a crystallization temperature (Tc) of 350° C. or lower, and a crystal-remelting temperature (Tr) of 450° C. or lower. The glass frits of the Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples can bond an adherend at relatively low treatment temperatures, i.e., 450° C. or lower. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frits of the Examples exhibits high thermal stress resistance and maintains high adhesion when, after being bonded, the device is placed under thermal cycling conditions.
Table 13 shows glass frits essentially consisting of (A) Ag2O, (B) V2O5, (C-1) MoO3, and (C-2) ZnO but having different mass ratios (Ag2O/V2O5) of component (A) to component (B). The glass frits were produced by a method similar to Example 1 except that the compositions shown in Table 11 were used, and evaluated in a manner similar to Example 1.















TABLE 13







1.80
1.95
2.18
2.60
3.20
3.50
3.70



Ag2O/V2O5
Example 87
Example 94
Example 54
Example 88
Example 89
Example 92
Example 93























(A)
(A) Ag2O: 231.7 g/mol
52.71
54.20
56.21
59.22
62.48
63.78
64.55


(B)
(B) V2O5: 181.9 g/mol
29.29
27.80
25.79
22.78
19.52
18.22
17.45


(C)
(C) MoO3: 143.9 g/mol
10.00
10.00
10.00
10.00
10.00
10.00
10.00



(C) ZnO: 81.4 g/mol
8.00
8.00
8.00
8.00
8.00
8.00
8.00



Total
100.00
100.00
100.00
100.00
100.00
100.00
100.00



Melt Temp (C.)
700
700
700
700
700
700
700



Dwell at melting temp. (C.)
15
15
15
15
15
15
15



Preheat Temp (C.)
550
550
550
550
550
550
550



Precrystallize (C.)
—
—
—
—
—
—
—


Tg
Tg (C.)
181.2
178.12
167.88
159.75
145.97
—
—



(mW)









TC
TC1 − Tg
70.15
76.15
87.11
54.44
41.31
—
—



TC1 (C.)
251.35
254.27
254.99
214.19
187.28
172.62
191.98



(J/g)
56.01
52.33
51.86
43.62
12.25
1.33




TC2 (C.)

296.64
295.49
313.91
267.61
288.41
285.58



(J/g)

0.27
0.91
7.22
3.12
11.38
10.03



TC3 (C.)




290.06





(J/g)




8.74




TR
TR1 (C.)
340.61
341.05
342.31
344.55
416.17
360.21
380.33



(J/g)
−15.98
−38.08
−78.99
−32.06
−7.09
−14.51
−14.05



TR2 (C.)




460.79
416.42
416.28



(J/g)




−18.47
−11.04
−12.76



TR3 (C.)





461.24
460.27



(J/g)





−27.33
−24.18



bach size
10 g
10 g
10 g
10 g
10 g
10 g
10 g



Melt pour
good
good
good
good
good
good
good









As shown in Table 13, the glass frits of these Examples having a mass ratio (Ag2O/V2O5) of component (A) to component (B) of 1.8 to 3.2 have a glass transition temperature (Tg) of 200° C. or lower, a crystallization temperature (Tc) of 150 to 320° C., and a crystal-remelting temperature (Tr) of 465° C. or lower. The glass frits of the Examples are easily melted at relatively low temperatures (e.g., 465° C. or lower). The glass frits of the Examples can be used in die attach materials, electrically conductive pastes, or sealing materials. A die attach material, electrically conductive paste, or sealing material containing the glass frit of the Examples can enhance adhesion by sufficiently wetting and spreading over the adhesive interface. The glass frits of the Examples recrystallize in low temperature ranges of 465° C. or lower, thereby bringing the state of the crystals closer to a eutectic state. A device that uses a die attach material, electrically conductive paste, or sealing material containing the glass frit of the Examples can exhibit high thermal stress resistance. When the glass frit has a mass ratio (Ag2O/V2O5) of component (A) to component (B) of less than 1.8, the glass frit is not vitrified. Furthermore, when the glass frit has a mass ratio (Ag2O/V2O5) of component (A) to component (B) of greater than 3.2, the crystallization temperature (Tc) will be a relatively low temperature of 200° C. or lower, and the crystal-remelting temperature (Tr) will be a relatively low temperature of around 360° C. In a device that uses a die attach material, electrically conductive paste, or sealing material containing a glass frit having a mass ratio (Ag2O/V2O5) of component (A) to component (B) of greater than 3.3, the glass frit may be melted and may not be able to maintain good adhesion when the device is placed under conditions where it is subjected to thermal cycles at relatively high temperatures.
INDUSTRIAL APPLICABILITY
The present invention is directed to a glass frit having a low melting point and not containing lead (Pb), arsenic (As), tellurium (Te), or antimony (Sb), which are toxic substances. The glass frit of the present invention has, for example, a glass transition temperature (Tg) of 300° C. or lower, a crystallization temperature (Tc) of 400° C. or lower, and a crystal-remelting temperature (Tr) of 500° C. or lower. The glass frit of the present invention is industrially useful since it can be used in die attach materials, sealing materials, electrically conductive pastes for forming electrodes, or the like that can be used in electronic components such as display devices or ceramic packages for housing integrated circuit devices, and that can be also used to bond an adherend that is extremely sensitive to heat.

## Claims

1. A glass frit which does not contain lead, arsenic, antimony or tellurium, the glass frit comprising (A) Ag2O, (B) V2O5, and (C) at least two first oxides consisting of a combination of at least two oxides selected from the group consisting of MoO3, ZnO and CuO.

2. The glass frit according to claim 1, wherein component (C) consists of a combination of oxides selected from the group consisting of MoO3 and ZnO; MoO3 and CuO; and ZnO and CuO.

3. The glass frit according to claim 1, wherein component (C) consists of a combination of MoO3, ZnO and CuO.

4. The glass frit according to claim 1, wherein the mass ratio (Ag2O/V2O5) of (A) to (B) is 1.8 to 3.2.

5. The glass frit according to claim 1, wherein (A) is in an amount of 40 to 70% by mass, (B) is in an amount of 10 to 40% by mass, and (C) is in an amount of 0.5 to 30% by mass, with respect to the total mass in terms of oxides.

6. The glass frit according to claim 5, wherein (C) is in an amount of 0.5 to 15% by mass, with respect to the total mass in terms of oxides.

7. The glass frit according to claim 1, further comprising (D) at least one second oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3 and Fe2O3.

8. The glass frit according to claim 7, wherein (D) is in an amount of greater than 0 to 15% by mass with respect to the total mass in terms of oxides.

9. A glass frit which does not contain lead, arsenic, antimony or tellurium, the glass frit consisting essentially of (A) Ag2O, (B) V2O5, and (C) at least one first oxide consisting of MoO3 or a combination of at least two oxides selected from the group consisting of MoO3, ZnO and CuO.

10. The glass frit according to claim 9, wherein (C) consists of two first oxides selected from the group consisting of MoO3, ZnO and CuO.

11. The glass frit according to claim 9, wherein (C) consists of MoO3.

12. The glass frit according to claim 9, wherein (C) consists of MoO3 and ZnO.

13. The glass frit according to claim 12, wherein a mass ratio (MoO3:ZnO) of MoO3 to ZnO in (C) is 12:1 to 1:12.

14. The glass frit according to claim 9, wherein (C) consists of MoO3 and CuO.

15. The glass frit according to claim 14, wherein a mass ratio (MoO3:CuO) of MoO3 to CuO in (C) is 12:1 to 1:10.

16. The glass frit according to claim 9, wherein (C) consists of ZnO and CuO.

17. The glass frit according to claim 16, wherein a mass ratio (ZnO:CuO) of ZnO to CuO in (C) is 12:1 to 1:12.

18. The glass frit according to claim 9, wherein (C) consists of MoO3, ZnO, and CuO.

19. The glass frit according to claim 18, wherein a mass ratio (MoO3:total amount of CuO and ZnO) of MoO3 to the total amount of ZnO and CuO in (C) is 12:1 to 1:12.

20. A glass frit which does not contain lead, arsenic, antimony or tellurium, the glass frit consisting essentially of (A) Ag2O; (B) V2O5; (C) at least one first oxide consisting of MoO3 or a combination of at least two oxides selected from the group consisting of MoO3, ZnO and CuO; and (D) at least one second oxide selected from the group consisting of SiO2, Al2O3, SnO, WO3 and Fe2O3.

21. The glass frit according to claim 18, wherein (C) consists of MoO3.