Source: http://www.google.com/patents/US7462900?dq=7,634,557
Timestamp: 2015-03-31 16:27:18
Document Index: 365034709

Matched Legal Cases: ['Application No. 2003', 'Application No. 2004', 'Application No. 1020014011708', 'Application No. 10', 'Application No. 10', 'Application No. 10', 'Application No. 10']

Patent US7462900 - Phase changeable memory devices including nitrogen and/or silicon - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsPhase-changeable memory devices and method of fabricating phase-changeable memory devices are provided that include a phase-changeable material pattern of a phase-changeable material that may include nitrogen atoms and/or silicon atoms. First and second electrodes are electrically connected to the phase-changeable...http://www.google.com/patents/US7462900?utm_source=gb-gplus-sharePatent US7462900 - Phase changeable memory devices including nitrogen and/or siliconAdvanced Patent SearchPublication numberUS7462900 B2Publication typeGrantApplication numberUS 12/039,156Publication dateDec 9, 2008Filing dateFeb 28, 2008Priority dateFeb 24, 2003Fee statusPaidAlso published asUS7115927, US7704787, US20040165422, US20060281217, US20080169457Publication number039156, 12039156, US 7462900 B2, US 7462900B2, US-B2-7462900, US7462900 B2, US7462900B2InventorsHorii Hideki, Bong-Jin Kuh, Yong-ho Ha, Jeong-hee Park, Ji-Hye YiOriginal AssigneeSamsung Electronics Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (85), Non-Patent Citations (6), Referenced by (16), Classifications (45), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetPhase changeable memory devices including nitrogen and/or silicon
US 7462900 B2Abstract
Phase-changeable memory devices and method of fabricating phase-changeable memory devices are provided that include a phase-changeable material pattern of a phase-changeable material that may include nitrogen atoms and/or silicon atoms. First and second electrodes are electrically connected to the phase-changeable material pattern and provide an electrical signal thereto. The phase-changeable material pattern may have a polycrystal line structure.
2. The device of claim 1, wherein the phase-changeable material pattern comprises (TeaSbbGe 100−(a+b))nN100−n and a≦80, 5≦b≦50, 75≦n≦99.75where a,b and 100−(a+b) are atomic percentages of the TeSbGe composition and n and 100−n are atomic percentages of the total composition.
4. A phase-changeable memory device, comprising:
5. The device of claim 4, wherein the variable resistor comprises (TeaSbbGe100−(a+b))nN100−n and a≦80, 5≦b≦50, 75≦n≦99.75, where x and 100−x are atomic percentages with respect to the AB composition and n and 100−n are atomic percentages with respect to the total composition.
a variable resistivity material having resistivity-increasing dopants therein that comprise from about 0.1% to about 25% of a total number of atoms in the variable resistivity material; and
first and second electrodes electrically coupled to the variable resistivity material.
7. The memory device of claim 6, wherein the variable resistivity material has a polycrystalline structure.
8. The memory device of claim 6, wherein the dopants comprise silicon atoms and/or nitrogen atoms.
9. The memory device of claim 8, wherein the nitrogen atoms included in the variable resistivity material are from about 0.1% to about 20% of a total number of atoms in the variable resistivity material.
10. The memory device of claim 9, wherein the silicon atoms are from about 0.25 to about 8 atomic percent and the nitrogen atoms from about 0.25 to about 10 atomic percent of the variable resistivity material.
11. The memory device of claim 6, wherein the variable resistivity material comprises Ge�Sb�Te�Si, As�Sb�Te�Si, As�Ge�Sb�Te�Si, Sn�Sb�Te�Si, In�Sn�Sb�Te�Si, Ag�In�Sb�Te�Si, 5A group element-Sb�Te�Si, 6A group element-Sb�Te�Si, 5A group element-Sb�Se�Si, and/or 6A group element-Sb�Se�Si.
12. The memory device of claim 6, wherein the variable resistivity material comprises (TeaSbbGe100−(a+b))nSi100−n, wherein a≦80, 5≦b≦50, 85≦n≦99.9, where a,b and 100−(a+b) are atomic percentages with respect to the TeSbGe composition and n and 100−n are atomic percentages with respect to the total composition.
13. The memory device of claim 8, wherein the variable resistivity material comprises (TeaSbbGe100−(a+b))nSicN100−(n+c), wherein a≦80, 5≦b≦50, 0.1≦c≦15, 80≦n≦99.9, where a,b and 100−(a+b) are atomic percentages with respect to the TeSbGe composition and n, c and 100−(n+c) are atomic percentages with respect to the total composition.
14. The memory device of claim 8, wherein the variable resistivity material comprises (TeaSbbGe100−(a+b))nSicN100−(n+c), wherein a≦80, 5≦b≦50, 0 25≦c≦8, 90≦n≦99.75, where a,b and 100−(a+b) are atomic percentages with respect to the TeSbGe composition and n, c and 100−(n+c) are atomic percentages with respect to the total composition.
15. The memory device of claim 6, wherein the variable resistivity material comprises AxB100−x, wherein component A is tellurium, selenium, sulfur, and/or polonium and component B is antimony, arsenic, germanium, tin, phosphorus, silver, oxygen, indium and/or bismuth and wherein x≦80 and x and 100−x are atomic percentages.
16. The memory device of claim 15, wherein the variable resistivity material comprises (AxB100−x)nSi100−n, wherein x≦80, 85≦n≦99.9, where x and 100−x are atomic percentages with respect to the AB composition and n and 100−n are atomic percentages with respect to the total composition.
17. The memory device of claim 15, wherein the variable resistivity material comprises (AxB100−x)nSicN100−(n+c), wherein x≦80, 65≦n≦99.8, 80≦n+c≦99.9, 0.1≦c≦15, where x and 100−x are atomic percentages with respect to the AB composition and n, c and 100−(n+c) are atomic percentages with respect to the total composition.
a variable resistivity material, wherein the variable resistivity material includes nitrogen atoms and further comprises AxB100−x, wherein component A comprises tellurium, selenium, sulfur and/or polonium, and component B comprises antimony, arsenic, germanium, tin, phosphorus, silver, oxygen, indium and/or bismuth and wherein x≦80 and x and 100−x are atomic percentages; and
19. The memory device of claim 18, wherein the variable resistivity material comprises (TeaSbbGe100−(a+b)nN100−n and a≦80, 5≦b≦50, 75≦n≦99.75 where a,b and 100−(a+b) are atomic percentages of the TeSbGe composition and n and 100−n are atomic percentages of the total composition.
a variable resistivity material doped with resistivity-increasing dopants to a level in a range from about 0.1% to about 15% by atomic percentage; and
21. The memory cell of claim 20, wherein the resistivity-increasing dopants include nitrogen.
22. The memory cell of claim 21, wherein the resistivity-increasing dopants include silicon. Description
The present application is a divisional of and claims priority from U.S. patent application Ser. No. 10/910,945, filed Aug. 4, 2004 now U.S. Pat. No. 7,402,851. U. S. patent application Ser. No. 10/910,945 is a continuation-in-part of and claims priority from U. S. Pat. application Ser. No. 10/781,597, filed Feb. 18, 2004 (now U.S. Pat. No. 7,115,927), which claims priority from Korean Patent Application No. 2003-11416, filed on Feb. 24, 2003, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entireties. The present application also claims priority under 35 U.S.C. �119 from Korean Patent Application No. 2004-12358, filed on Feb. 24, 2004, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.
Semiconductor memory devices are typically categorized into volatile memory devices and non-volatile memory devices depending on whether data can be conserved or not when power is removed from the device. Volatile memory devices include D-RAM devices and S-RAM devices and non-volatile memory devices include flash memory devices. These memory devices, typically, indicate logic �0� or �1� according to the presence of stored charge.
Accordingly, new memory devices have been developed, having non-volatile, random access characteristics and a simple structure. Such devices include phase-changeable memory devices. The phase-changeable memory device typically utilizes a phase-changeable material that changes crystalline structure thereof depending on the provided heat. Conventionally, the phase-changeable material is a chalcogen compound including germanium (Ge), antimony (Sb) and tellurium (Te) (i.e., CST or Ge�Sb�Te). When current is applied to the phase-changeable material layer to heat the GST, the crystalline state of a predetermined portion of the GST changes depending on the provided amount and time of the current. The resistance varies according to the state of crystal, such that logical information can be determined by detecting the difference of the resistance. In this case, a crystalline state has low resistance and an amorphous state has high resistance.
If GST is heated up to a melting point (about 610� C.) by applying high current flux to the GST for a short time (1-10 ns) and cooled quickly in a short time (1 ns or less), the heated portion of the GST becomes amorphous (e.g. a reset state). If GST is heated up to maintain a crystalline temperature (about 450� C.) lower than the melting point temperature by applying relatively low current flux for a long time, e.g., about 30-50 ns, (a resistant heating) and cooled down, the heated portion of the GST becomes crystalline (e.g., a set state).
A representative chalcogen compound includes, for example, Ge22Sb22Te56 having three ingredients of tellurium Te, antimony Sb and germanium Ge. In particular embodiments of the present invention, the tellurium Te has a concentration ranging from at least about 20% to about 80% of the total number of atoms in the composition. The antimony Sb has a concentration ranging from about 5% to 50% of the of the total number of atoms in the composition and the remainder is germanium Ge. That is, this configuration can be characterized as TeaSbbGe100−(a+b) (20≦a≦80 and 5≦b≦50), where the subscripts are atomic percentages that total 100% of the constituent elements. References to Ge�Sb�Te as a chalcogen compound may have the above configuration if there is no mention of a different configuration.
The compound may include two, three, four, five or more ingredients including at least one chalcogen element. As used herein, a chalcogen element refers to an element in the same column as oxygen in the periodic table of elements. That is, the compound may include A and B in the ratio AxB100−x, wherein component A is at least one chalcogen, such as tellurium Te, selenium Se, sulfur S, and/or polonium Po, and component B is antimony Sb, arsenic As, germanium Ge, tin Sn, phosphate P, S silver Ag, oxygen O, indium In and/or bismuth Bi. For example, the compound may be Ge�Sb�Te, As�Sb�Te, As�Ge�Sb�Te, Sn�Sb�Te, In�Sn�Sb�Te, Ag�In�Sb�Te, 5A group element-Sb�Te, 6A group element-Sb�Te, 5A group element-Sb�Se, 6A group element-Sb�Se, etc.
Therefore, in certain embodiments of the present invention, the phase-changeable material doped with nitrogen may be characterized as (AxB100−x)nN100−n (x≦80 and 75≦n≦99.75) where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Thus, for example, the subscript x may be a percentage of the total atoms in the composition AB and the subscript n may be a percentage of the total atoms in the composition (AB)N. The chalcogen compound may, for example, include tellurium Te, germanium Ge, and antimony Sb. In this case, the phase-changeable material may be characterized as (Te�Sb�Ge)nN100−n (75≦n≦99.75) and the configuration of the Te�Sb�Se may be the same as explained above. That is, the phase-changeable material according to certain embodiments of the present invention may be characterized as (TeaSbbGe100−(a+b))nN100−n (20≦a≦80, 5≦b≦50 and 75≦n≦99.75), where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript.
In further embodiments of the present invention, the phase-changeable material doped with silicon may be characterized as (AxB100−x)nSi100−n (x≦80 and 85≦n≦99.9) where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. For example, when the chalcogen compound includes tellurium Te, germanium Ge, antimony Sb, the phase-changeable material may be characterized as (Te�Sb�Ge)nSi100−n (85≦n≦99.9) and the configuration of Te�Sb�Ge is the same as explained above. That is, the phase-changeable material may be characterized as (TeaSbbGe100−(a+b))nSi100−n (20≦a≦80, 5≦b≦50, and 85≦n≦99.9) where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript.
In further embodiments of the present invention, the phase-changeable material doped with nitrogen and silicon may include (AxB100−x)nSicN100−(n+c) (x≦80, 65≦n≦99.8, 80≦n+c≦99.9, and 0.1≦c≦15 where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. In particular embodiments of the present invention, x≦80, 82≦n≦99.5, 90≦n+c≦99.75 and 0.25≦c≦8. For example, if the chalcogen compound includes tellurium Te, antimony Sb and germanium Ge, the phase-changeable material layer may be characterized as (Te�Sb�Ge)nSicN100−(n+c) (0.1≦c≦15, and 80≦c+n≦99.9) and in particular embodiments, 0.25≦c≦8, and 90≦c+n≦99.75, and the configuration of the Te�Sb�Ge is the same as explained above. Namely, the phase-changeable material layer may be characterized as (TeaSbbGe100−(a+b))nSicN100−(n+c) (20≦a≦80, 5≦b≦50, 0.1≦c≦15, and 80≦c+n≦99.9) where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript.
The phase-changeable material is interposed between first and second electrodes and supplied with an electrical signal (a current pulse) through the electrodes. The first and second electrodes may be a conductive material containing nitrogen N, a conductive material containing carbon C, titanium Ti, tungsten N, molybdenum Mo, tantalum Ta, titanium silicide TiSi, tantalum silicide TaSi and/or a combination thereof.
In one embodiment of the present invention, the first and/or second conductive electrodes may also further include one of aluminum Al, aluminum-copper alloy Al�Cu, aluminum-copper-silicon alloy Al�Cu�Si, tungsten silicide WSi, copper Cu, tungsten titanium TiW and/or a combination thereof.
The conductive material containing nitrogen may be titanium nitride TiN, tantalum nitride TaN, molybdenum nitride MoN, niobium nitride NbN, titanium silicon nitride TiSiN, titanium aluminum nitride TiAlN, titanium boron nitride TiBN, zirconium silicon nitride ZrSiN, tungsten silicon nitride WSiN, tungsten boron nitride WBN, zirconium aluminum nitride ZrAlN, molybdenum silicon nitride MoSiN, molybdenum aluminum nitride WON, tantalum silicon nitride TaSiN, tantalum aluminum nitride TaAlN, titan oxide nitride TiON, titanium aluminum oxide nitride TiAlON, tungsten oxide nitride WON and/or tantalum oxide nitride TaON. The conductive material containing carbon includes a conductive carbon such as graphite.
The phase-changeable material in a polycrystalline state or containing nitrogen ingredients may be formed using a sputtering technique. For example, the sputtering technique may use a nitrogen gas as a source gas and an argon gas (an inert gas) as a carrier gas, targeting the chalcogen compound. In addition, the sputtering may be carried out tinder temperature conditions at which the phase-changeable material is in a polycrystalline state having small grains. For example, the temperature may range from about 100� C. to about 350� C.
FIG. 2 is a graph showing resistivity of GST containing nitrogen (Ge�Sb�Te�N) according to concentrations of the nitrogen.
FIG. 3 is a graph showing resistivities of conventional Ge�Sb�Te and Ge�Sb�Te�N according to certain embodiments of the present invention.
FIG. 15 is a graph showing a resistivity of silicon doped Ge�Sb�Te (Se�Sb�Te�Si) according to an amount of silicon.
FIG. 17 is a graph showing a resistivity of silicon and nitrogen doped Ge�Sb�Te�Si�N according to a content of nitrogen.
The present invention will now be described more fully with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the size or thickness of layers and regions are exaggerated for clarity. Like numbers refer to like elements. As used herein the term �and/or� includes any and all combinations of one or more of the associated listed items.
The phase-changeable memory device, as illustrated in FIG. 1, utilizes phase-changeable materials whose crystalline state is varied between a polycrystalline state and an amorphous state depending on applied heat. That is, when a high current pulse is applied to the phase-changeable materials for a short time (e.g., 1 ns-10 ns), the phase-changeable materials change into an amorphous state (reset state) having a high resistivity, but when a low current plus is applied for a long time (e.g., 30 ns-50 ns), the phase-changeable materials changes into the crystalline state (set state) having a low resistivity. Thus, if the phase-changeable material layer is heated to a temperature higher than a melting point (Tm) thereof (a resistor heated by a current pulse) and then cooled for a short time (T1), the phase-changeable material layer becomes amorphous (referring to a curve {circle around (1)}). If the phase-changeable material layer is heated to a temperature lower than the melting temperature (Tm) but higher than the crystallization temperature (Tc) (a resistor heated by a current pulse), maintained for a specific time T2 longer than T1 and cooled, the phase-changeable material becomes crystalline (referring to a curve {circle around (2)}.
The phase-changeable material layer according to certain embodiments of the present invention contains nitrogen atoms and/or silicon atoms. In some embodiments, the nitrogen atoms and/or silicon atoms exist not only inside the small grains (inside crystals) but also at the interface of the grains of the polycrystalline phase-changeable material. Due to the nitrogen atoms and/or silicon atoms, the resistivity of the phase-changeable material layer increases, resulting in a decrease of the current pulse required for changing the crystalline state of the phase-changeable material layer. The nitrogen and/or silicon atoms suppress the grain growth of the phase-changeable material, such that the grains of the phase-changeable material layer may be small. As the concentration of the nitrogen and/or silicon increases, the size of the crystal decreases. For example, in certain embodiments of the present invention, the phase-changeable material layer has a polycrystalline state having grains less than about 100 nm. In particular embodiments of the present invention, the phase-changeable material layer has a grain size of about 40 mn grains or smaller.
Chalcogen compounds can be characterized as AxB100−x, wherein component A includes a chalcogen, such as tellurium Te, selenium Se, sulfur S, and/or polonium Po, and component B is at least one of antimony Sb, arsenic As, germanium Ge, tin Sn, phosphate P, silver Ag, oxygen O, indium In and/or bismuth Bi. For example, the chalcogenide compound may be Ge�Sb�Te, As�Sb�Te, As�Ge�Sb�Te, Sn�Sb�Te, In�Sn�Sb�Te, Ag�In�Sb�Te, 5A group element-Sb�Te, 6A group element-Sb�Te, 5A group element-Sb�Se, 6A group element-Sb�Se, etc.
In certain embodiments of the present invention, the phase-changeable material layer can be a chalcogen compound containing nitrogen, such as a nitrogen doped chalcogen compound, characterized as (AxB100−x)nN100−n, wherein x≦80, 75≦n≦99.75 where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Namely, the phase-changeable material layer contains from about 0.25 to about 25% nitrogen atoms with respect to the total number of atoms of the ingredients. If the chalcogen compound includes Te, Sb, Ge, the phase changeable material may be characterized as (Te�Sb�Ge)nN100−n, wherein 75≦n≦99.75 and the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Namely, the phase-changeable material can be characterized as (TeaSbbGe100−(a+b))nN100−n, wherein a≦80, 5≦b≦50, 75≦n≦99.75 where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript.
In certain embodiments of the present invention, the phase-changeable material layer can be a silicon doped chalcogen compound characterized as (AxB100−x)nSi100−n, wherein x≦80, 85≦n≦99.9 and the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Namely, the phase-changeable material layer contains from about 0.1 to about 15% silicon atoms with respect to the total number of atoms of the ingredients. If the chalcogen compound includes Te, Sb, Ge, the phase changeable material may be characterized in (Te�Sb�Ge)nS100−n, wherein 85≦n≦99.9 and the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Namely, the phase-changeable material can be characterized as (TeaSbbGe100−(a+b))nSi100−n, wherein a≦80, 5≦b≦50, 85≦n≦99.9 where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript.
In certain embodiments of the present invention, the phase-changeable material layer can be a chalcogen compound containing nitrogen and silicon, such as a nitrogen and silicon doped chalcogen compound, characterized as (AxB100−x)nSicN100−(n+c), wherein x≦80, 65≦n≦99.8, 80≦n+c≦99.9, 0.1≦c≦15 and the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Namely, the phase-changeable material layer contains from about 0.1 to about 15% silicon atoms and from about 0.1 to 20% nitrogen atoms with respect to the total number of atoms of the ingredients. In particular embodiments of the present invention, the phase-changeable material may contain from about 0.25 to about 8% silicon atoms and from about 0.25 to 10% nitrogen atoms. Thus, in particular embodiments of the present invention, the chalcogen compound containing nitrogen and silicon may be characterized as (AxB100−x)nSicN100−(n+c), wherein x≦80, 82≦n≦99.5. 90≦n+c≦99.75, 0.25≦c≦8 and the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. If the chalcogen compound includes Te, Sb, Ge, the phase changeable material may be characterized as (Te�Sb�Ge)nSicN100−(n+c), wherein 0.1≦c≦15, 80≦n≦99.9 and, in some embodiments, 0.25≦c≦8, 90≦n≦99.75 where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. Namely, the phase-changeable material can be characterized as (TeaSbbGe100−(a+b))nSicN100−(n+c), wherein a≦80, 5≦b≦50, 0.1≦c≦15, 80≦n≦99.9 and in some embodiments, a≦80, 5≦b≦50, 0.25≦c≦8, 90≦n≦99.75 where the subscripts are atomic percentages that total 100% of the constituent elements associated with the respective subscript. A resistivity of the phase-changeable material increases as an amount of silicon and nitrogen becomes larger.
FIG. 2 is a graph showing resistivity of GST containing nitrogen atoms (Ge�Sb�Te�N) according to concentrations of the nitrogen. A parallel axis in the FIG. 2 refers to atomic percent of the nitrogen atoms contained in the GST, and a vertical axis refers to resistivity (Ωcm). Referring to FIG. 2, the resistivity of the GST increases as the concentration of nitrogen atoms.
FIG. 3 is a graph showing resistivity of conventional Ge�Sb�Te and Ge�Sb�Te�N according to certain embodiments of the present invention according to annealing temperatures. The horizontal axis refers to an annealing temperature (� C.), and the vertical axis refers to resistivity (Ωcm). In FIG. 3, -●- represents a resistivity of GST containing 7 atomic percent nitrogen and -□- represents a resistivity of conventional GST. Referring to FIG. 3, the resistivity of conventional Ge�Sb�Te reduces to about 2 mΩcm but the resistivity of GST containing 7% nitrogen atoms is measured to be greater that that of conventional GST (about 20 mΩcm). That is, the resistivity of the GST containing nitrogen atoms according to embodiments of the present invention increases about 10 times as high as the conventional one.
FIG. 4 is a transmission electron microscopy (TEM) picture showing a crystalline state of the conventional GST and a crystalline state of the GST containing 7% nitrogen atoms according to certain embodiments of the present invention after 500� C. annealing. The upper TEN picture of FIG. 4 shows a crystalline state of a conventional GST and the lower one shows a crystalline state of GST containing nitrogen atoms according to certain embodiments of the present invention. The pictures show the conventional GST has a mono-crystalline state of which grain size is about more than 100 nm but the GST containing nitrogen has a polycrystalline state of which the grains are about 40 nm or smaller.
The first electrode 119 is contact-plug-shaped and penetrates a specific region of the lower intermetal dielectric layer 115. The phase-changeable material patter 121 is disposed on the lower intermetal dielectric layer 115 and the first electrode 119 so as to be connected to the first electrode 119. The second electrode 123 is disposed on a surface of the phase-changeable material pattern 121. The conductive plug 128 penetrates a specific region of the upper interconnection dielectric layer 125 so as to be connected to a portion of the second electrode 123. The upper interconnection 129 is disposed on the upper dielectric layer 125 so as to be connected to the conductive plug 128.
As described above, the phase-changeable material pattern 121 has a high resistivity because of its polycrystalline state has a plurality of small grains. The phase-changeable material pattern 121 may be a chalcogenide compound containing nitrogen. For example, the phase-changeable material pattern 121 may be any one of Ge�Sb�Te�N, As�Sb�Te�N, As�Ge�Sb�Te�N. Sn�Sb�Te�N, In�Sn�Sb�Te�N, a 5A group element-Sb�Te�N, a 6A group element-Sb�Te�N, a 5A group-Sb�Se�N, and/or a 6A group-Sb�Se�N. An amount of the nitrogen atoms may be from about 0.25% to about 25% with respect to the total number of atoms of the phase-changeable material pattern. Resistivity of the phase-changeable material layer according to concentrations of the nitrogen atoms is illustrated in FIG. 2. As seen in FIG. 2, the resistivity increases as the concentration of the nitrogen atoms increases.
The first electrode 119 and/or the second electrode 123 may be a conductive material containing nitrogen, a conductive material containing carbon C, titanium Ti, tungsten NV, molybdenum Mo, tantalum Ta, titanium silicide TiSi, tantalum silicide TaSi and/or a combination thereof. The conductive material containing nitrogen may be titanium nitride TiN, tantalum nitride TaN, molybdenum nitride MoN, niobium nitride NbN, titanium silicon nitride TiSiN, titanium aluminum nitride TiAlN, titanium boron nitride TiBN, zirconium silicon nitride ZrSiN, tungsten silicon nitride WSiN, tungsten boron nitride WBN, zirconium aluminum nitride ZrAlN, molybdenum silicon nitride MoSiN, molybdenum aluminum nitride MoAlN, tantalum silicon nitride TaSiN, tantalum aluminum nitride TaAlN, titan oxide nitride TiON, titan aluminum oxide nitride TiAlON, tungsten oxide nitride WON and/or tantalum oxide nitride TaON. The conductive material containing carbon may include graphite, for instance.
The conductive plug 127 electrically connecting the upper interconnection 129 and the second electrode 123 and may be formed of aluminum Al, aluminum-copper alloy Al�Cu, aluminum-copper-silicon alloy Al�Cu�Si, tungsten silicide WSi, copper Cu, tungsten titanium TiW, tantalum Ta, molybdenum Mo, tungsten W, etc. The upper interconnection 129 may serve as a data line (a bit line) transferring logic information stored in the variable resistor 124. The upper interconnection 129 may be formed of aluminum Al, aluminum-copper alloy Al�Cu, aluminum-copper-silicon alloy Al�Cu�Si, tungsten suicide WSi, copper Cu, tungsten titanium TiW, tantalum Ta, molybdenum Mo, tungsten W, etc.
In a write operation for writing logic information (e.g., �0� (a high resistance state) or �1� (a low resistance state)) to the variable resistor Rv 124, a signal sufficient to turn on the access transistor Ta is applied to the word line WL and a bit line BL is grounded. Then, a signal is input to the lower interconnection IL. The signal input to the lower interconnection IL corresponds to a current pulse having a magnitude and duration corresponding to the logic information to be written. Therefore, current flows between the lower interconnection IL and the bit line BL through the variable resistor Rv. The phase-changeable material pattern of the variable resistor Rv changes the crystalline state thereof based on the current pulse, thereby changing a resistance of the variable resistor Rv.
Referring to FIG. 9A, a conventional MOS field effect transistor (MOSFET) is fabricated by forming a field isolation region 103 and a transistor 109 in a semiconductor substrate 100. The field isolation region 103 is an insulation region to define an active region, and may be formed by local oxidation of silicon (LOCOS) or a shallow trench isolation technique. The transistor 109 is formed on the semiconductor substrate 100 and includes a gate electrode 105, a source region 107 b and a drain region 107 a. The gate electrode 105 extends along one direction and the source and drain regions 107 b and 1007 a are formed at both sides of the gate electrode 105. An active region under the gate electrode 105 serves as a current path (channel) between the source and drain region 107 b and 107 a. A gate-insulating layer is provided between the gate electrode 105 and the channel region.
FIG. 9C illustrates a process for forming a lower interconnection 113 a. The lower interconnection 113 a is a conductive interconnection electrically connected to the drain region 107 a of the transistor 109. For example, the lower interconnection 113 a may extend parallel to the gate electrode 105. In the embodiments illustrated in FIG. 9C, the lower interconnection 113 a is formed by a dual damascene process. In particular, the interlayer dielectric layer 111 is patterned to form an interconnection groove 112 a and contact hole 112 a′ exposing the drain region 107 a at a specific region of the interconnection groove 112 a. The groove 112 a and the contact hole 112 a′ are substantially filled with conductive materials to form the lower interconnection 113 a electrically connected to the drain region 107 a. In this case, contact pads 113 b electrically connected to the source regions 107 b are also formed during the formation of the lower interconnection 113 a. That is, while forming the interconnection groove 112 a and the contact hole 112 a′, openings for contact pads 112 b and contact holes 112 b′ exposing the source region 107 b are formed. The contact holes 112 b′ are connected to the openings 112 b. While the groove 112 a and the contact hole 112 a′ are filled with conductive material, the openings 112 b and the contact holes 112 b′ are also substantially filled with the conductive material. The contact pad 113 b electrically connects the variable resistor 124 of FIG. 9F to the source region 107 b.
The first electrode 119 may be a conductive material containing nitrogen, a conductive material containing carbon C, titanium Ti, tungsten W, molybdenum Mo, tantalum Ta, titanium suicide TiSi, tantalum silicide TaSi, and/or a combination thereof. The first electrode 119 may be formed by a chemical vapor deposition, a physical vapor deposition, an atomic layer vapor disposition, etc. The conductive material containing nitrogen may be titanium nitride TiN, tantalum nitride TaN, molybdenum nitride MoN, niobium nitride NbN, titanium silicon nitride TiSiN, titanium aluminum nitride TiAlN, titanium boron nitride TiBN, zirconium silicon nitride ZrSiN, tungsten silicon nitride WSiN, tungsten boron nitride WBN, zirconium aluminum nitride ZrAlN, molybdenum silicon nitride MoSiN, molybdenum aluminum nitride MoAlN, tantalum silicon nitride TaSiN, tantalum aluminum nitride TaAlN, titanium oxide nitride TiON, titanium aluminum oxide nitride TiAlON, tungsten oxide nitride WON and/or tantalum oxide nitride TaON.
Referring again to FIG. 9E, a phase-changeable material layer 121 and a second electrode layer 123 are formed on the lower intermetal interconnection 115 after the first electrode 119 is formed. The phase-changeable material layer 121 contains nitrogen atoms. For example, the phase-changeable material layer 121 may be formed by a sputtering method using nitrogen gas and argon gas as a carrier gas, targeting chalcogenide compounds. In this case, the phase-changeable material layer 121 may be formed at about 100-350� C., for instance. According to certain embodiments of the present invention, the phase-changeable material layer 121 has a polycrystalline state that includes a plurality of small grains of about 100 nm or lesser. In particular embodiments, the phase-changeable material layer 121 has a grain size of about 40 nm or lesser. The phase-changeable material layer 121 includes about 0.25 to about 15 atomic percent nitrogen atoms. The chalcogen compounds may be formed of, for example, Ge�Sb�Te, As�Sb�Te, As�Ge�Sb�Te, Sn�Sb�Te, In�Sn�Sb�Te, Ag�In�Sb�Te, a 5A group element-Sb�Te, a 6A group element-Sb�Te, a 5A group element-Sb�Se, a 6A group-Sb�Se, etc. Therefore, the phase-changeable material layer 121 may be formed of Ge�Sb�Te�N, As�Sb�Te�N, As�Ge�Sb�Te�N, Sn�Sb�Te�N, In�Sn�Sb�Te�N, Ag�In�Sb�Te�N, a 5A group element-Sb�Te�N, a 6A group element-Sb�Te�N, a 5A group element-Sb�Se�N, a 6A group element-Sb�Se�N, etc.
Exemplary embodiments of forming the Ge�Sb�Te�N using sputtering will be explained hereinafter. The Ge�Sb�Te�N is formed to a thickness of from about 100 to about 1000 Å, targeting Ge�Sb�Te, under the condition of 10 mm Torr argon, about 1 mm Torr nitrogen, about 500 W DC power and about 100-350� C. The phase-changeable material layer has a polycrystalline state that includes a plurality of small grains (40 nm or lesser) as shown in FIG. 4.
The conductive plug 127 may be formed of aluminum Al, aluminum copper alloy Al�Cu, aluminum copper silicon alloy Al�Cu�Si, tungsten silicide WSi, titanium Ti, tungsten W, molybdenum Mo, tantalum Ta, titanium tungsten TiW, copper Cu, etc. by physical vapor deposition, chemical vapor deposition, etc. The upper interconnection 129 may also be formed of the same material as the conductive plug 127.
Referring to FIG. 10 b, a conductive material layer is formed on the upper intermetal dielectric layer 125 and the second electrode 123 and then patterned to form an upper interconnection 129. The upper interconnection 129 may be formed of aluminum Al, aluminum-copper alloy Al�Cu, aluminum-copper-silicon alloy Al�Cu�Si, tungsten silicide WSi, titanium Ti, tungsten W, molybdenum Mo, tantalum Ta, titanium tungsten TiW, copper Cu, etc. by physical vapor deposition, chemical vapor deposition, etc. The upper interconnection 129 directly contacts with the second electrode 123.
The phase-changeable material pattern 121 has a polycrystalline state with a plurality of small grains, such that resistivity thereof may be high. In certain embodiments of the present invention, the phase-changeable material pattern 121 is a chalcogenide compound doped with nitrogen atoms. For example, the phase-changeable material pattern 121 may be Ge�Sb�Te�N, As�Sb�Te�N, As�Ge�Sb�Te�N, Sn�Sb�Te�N, In�Sn�Sb�Te�N, a 5A group element-Sb�Te�N, a 6A group element-Sb�Te�N, a 5A group element-Sb�Se�N and/or a 6A group element-Sb�Se�N. An amount of the nitrogen atoms may be from about 0.25 to about 25% with respect to a total number of atoms of the ingredients included in the phase-changeable material pattern.
A First electrode material layer is deposited on the contact plug 116 and the lower intermetal dielectric layer 115 and then patterned to form a first electrode layer 119. The first electrode 119 covers the contact plug 116. An upper intermetal dielectric layer 125 is formed on the surface of the semiconductor substrate. The tipper intermetal dielectric layer 125 is patterned to form a contact hole 225 exposing the first electrode 119. A phase-changeable material layer is formed in the contact hole 225 and on the upper intermetal dielectric layer 125. The phase-changeable material layer 121 contains nitrogen atoms. For example, the phase-changeable material layer 121 may be formed by a sputtering method targeting chalcogen compounds, using argon gas as a carrier gas and nitrogen gas. The phase-changeable material layer 121 may be formed in a temperature range of from about 100� C. to about 350� C.
Referring to FIG. 15, the resistivity of (Ge�Sb�Te)99.9 Si0.1 including about 0.1% silicon atoms is about 20 mΩ cm. This is increased compared to the resistivity (i.e., 7 mΩ cm) of a conventional three-element chalcogen compound (Ge�Sb�Te). It is believed that, as the content of silicon increases a size of grain in the chalcogen compound decreases gradually aid the chalcogen compound becomes closer to an amorphous state. Therefore, the resistivity of the chalcogen compound increases.
A method of fabricating a Ge�Sb�Te�Si layer will be explained as one example of a chalcogen compound containing silicon. The chalcogen compound containing silicon is formed by a sputtering technique. That is, targeting a silicon-chalcogen compound, the sputtering is carried out using an argon gas of about 30 sccm to about 100 sccm and a nitrogen gas of about 1 sccm to about 10 sccm, in a temperature range of about 100� C. to 350� C. with a power of about 100 watts to about 2000 watts.
A method of forming a Ge�Sb�Te�Si�N layer will be explained as one example of a chalcogen compound containing silicon and nitrogen. That is, targeting a silicon-chalcogen compound (Ge�Sb�Te�Si) including silicon atoms of about 1% to 8%, the sputtering is carried out using an argon gas of about 30 sccm to about 200 sccm and a nitrogen gas of about 0.1 sccm to about 20 sccm, in a temperature range of about 100� C. to about 350� C. with a power of about 100 watts to about 2000 watts.
FIG. 17 is a graph illustrating a resistivity of the Ge�Sb�Te�Si�N according to contents of nitrogen. A resistivity is measured with an increasing amount of nitrogen atoms doped into a Ge�Sb�Te layer that is doped with silicon atoms of 3%.
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