Source: https://patents.google.com/patent/US7192888?oq=6373188
Timestamp: 2018-03-23 04:33:55
Document Index: 593537889

Matched Legal Cases: ['art.\n11', 'art.\n18', 'art.\n19', 'art.\n30', 'art.\n35', 'art.\n50', 'art.\n54', 'Application No. 04']

US7192888B1 - Low selectivity deposition methods - Google Patents
Low selectivity deposition methods Download PDF
US7192888B1
US7192888B1 US09643004 US64300400A US7192888B1 US 7192888 B1 US7192888 B1 US 7192888B1 US 09643004 US09643004 US 09643004 US 64300400 A US64300400 A US 64300400A US 7192888 B1 US7192888 B1 US 7192888B1
US09643004
A deposition method includes forming a nucleation layer over a substrate, forming a layer of a first substance at least one monolayer thick chemisorbed on the nucleation layer, and forming a layer of a second substance at least one monolayer thick chemisorbed on the first substance. The chemisorption product of the first and second substance may include silicon and nitrogen. The nucleation layer may comprise silicon nitride. Further, a deposition method may include forming a first part of a nucleation layer on a first surface of a substrate and forming a second part of a nucleation layer on a second surface of the substrate. A deposition layer may be formed on the first and second parts of the nucleation layer substantially non-selectively on the first part of the nucleation layer compared to the second part. The first surface may be a surface of a borophosphosilicate glass layer. The second surface may be a surface of a rugged polysilicon layer. The first and second part of the nucleation layer may be formed simultaneously.
This invention relates to methods of atomic layer deposition and methods of low selectivity chemical vapor deposition.
It can be seen that a need exists for an ALD method that forms a layer without, introducing intolerable defects into the material.
One aspect of the invention provides a deposition method that includes forming a nucleation layer over a substrate, forming a layer of a first substance at least one monolayer thick chemisorbed on the nucleation layer, and forming a layer of a second substance at least one monolayer thick chemisorbed. on the first substance. A chemisorption product of the first and second substance may include silicon and nitrogen, or aluminum and oxygen, or tantalum and oxygen. Also, the nucleation layer may comprise silicon nitride, aluminum oxide, or tantalum oxide. A thickness of the. nucleation layer may be less than about 20 Angstroms.
In another aspect of the invention, a low selectivity deposition method includes forming a first part of a nucleation layer on a first surface of a substrate and forming a second part of a nucleation layer. on a second surface of a substrate. A deposition layer may then be formed on the first and second parts of the nucleation layer substantially non-selectively on the first part of the nucleation layer compared to the second part. Substantially non-selective deposition occurs even though the first and second surfaces of the substrate exhibit a property of the deposition layer forming less readily on the first surface compared to the second surface. The deposition layer may comprise a monolayer of a first chemisorbed specie. The deposition layer may be formed by chemical vapor deposition or atomic layer deposition. The first and second part of the nucleation layer may be formed simultaneously. Also, the nucleation layer may form substantially non-selectively on the first surface of the substrate compared to the second surface. Further, a thickness of the first part of the nucleation layer may be. greater than 50% of a thickness of the second part, or even greater than 80% of the thickness of the second part. The first surface of the substrate may exhibit a property of chemisorbing the first specie at a slower rate compared, to the second surface.
ALD is often described as a self-limiting process, in that a finite number of sites exist on a substrate to which the first specie may form chemical bonds. The second specie might only bond to the first specie ad thus may also be self-limiting. Once all of the finite number of sites on a substrate are bonded with a first specie, the first specie will often not bond to other of the first specie already bonded with the substrate. However, process conditions can be varied in ALD as discussed below to promote such bonding and render ALD not self-limiting. Accordingly, ALD may also encompass a specie forming other than one monolayer at a time by stacking of a specie, forming a layer more than one atom or molecule thick. The various aspects of the present invention described herein are applicable to any circumstance where ALD may be desired. A few examples of materials that may be deposited by ALD include silicon nitride, zirconium oxide, tantalum oxide, aluminum oxide, and others. Examples of specie pairs for ALD of silicon nitride include NH3/SiHCl3 and others.
There can be at least one advantage of providing a nucleation layer over a substrate prior to performing some types of deposition, for example ALD. The nucleation layer may operate to provide at least somewhat uniform surface properties for the deposition and decrease thickness variations such as shown in FIG. 2. Even so, a nucleation layer may interface between a substrate. and a subsequently deposited deposition layer in a manner that only insignificantly influences the overall properties of the combined nucleation and deposition layer. That is, a deposition layer deposited directly on a substrate without a nucleation layer generally will possess some designated purpose or designated property. A nucleation layer may be selected such that only an insignificant impact is imposed upon the desired purpose or property. Accordingly, a nucleation layer may find advantageous use even in circumstances where a substrate possesses both a homogeneous composition and homogeneous surface properties. Such a nucleation layer may interface between a substrate and a deposition layer to enhance the rate of formation of the deposition layer or to otherwise provide an advantageous property or result. For example, a first monolayer of a first chemisorbed specie may form more rapidly over BPSG if a nucleation layer is first formed.
In addition to composition and surface properties, the thickness of a nucleation layer may also influence its suitability. At times, ALD is selected with the desire to form high quality very thin layers of material. A nucleation layer may be selected that only insignificantly impacts the deposition layer. However, as the thickness of a nucleation layer increases and approaches or exceeds the thickness of a deposition layer, the potential advantages of selecting ALD for forming a layer of the material may be diminished. At the optimum, a nucleation layer having a thickness of only one atom or molecule may be formed to minimize any potential impact. However, a more thick nucleation layer may also ii provide little impact. Accordingly, a thickness of a nucleation layer may comprise less than about 20 Angstroms. Further, the thickness may comprise less than about 6 Angstroms. Still further, the thickness may comprise about 2.5 Angstroms. A monolayer of silicon nitride may comprise about 2.5 Angstroms.
One advantage of the present invention is that substantially nonselective formation of a nucleation layer may occur even though ALD on the same surface occurs selectively, that is, at a greater than 2 to 1 ratio of deposition rate. Such a deposition may produce a deposition layer having a thickness over the first surface that is less than 50% of the thickness over the second surface.
In accordance with the present aspect of the invention, observations indicate that increasing temperature or pressure or both can produce the effect of reducing the selectivity of an otherwise selective monolayer formation step. In the various aspects of the invention, temperature may remain below about 550 Celsius (° C.) and pressure may remain below about 20 Torr. The increased temperature, pressure, or both correspondingly increases the likelihood that a deposition specie will chemisorb substantially non-selectively on the first and second surfaces of the substrate as described above and shown in FIG. 3. Even though such a process regime risks defective monolayer formation, such process may be used to form a nucleation layer by ALD. The deposition layer may be formed in a traditional ALD process regime at lower temperature and pressure. For example, traditional ALD of silicon nitride may occur at a temperature of from about 400° C. to about 550° C. and a pressure of less than about 100 milliTorr. Different ranges are also conceivable, as determinable by those skilled in the art, depending on deposition precursors, nucleation layer composition, surface properties, and other factors. Depending on the desired properties of the deposition layer, such layer may also be formed by ALD outside the traditional ALD process regime.
As one example, U.S. patent application Ser. No. 09/619,449 filed Jul. 19, 2000 by Garo J. Derderian and Gurtej S. Sandhu entitled “Deposition Methods” and assigned to Micron Technologies, Inc. discloses a nontraditional ALD process and is herein incorporated by reference. Derderian et al. describe a deposition method including contacting a substrate with a first initiation precursor and forming a first portion of an initiation layer on the substrate. At least a part of the substrate is contacted with a second initiation precursor different from the first initiation precursor and a second portion of the initiation layer is formed on the substrate. The invention may include simultaneously contacting a substrate with a plurality of initiation precursors, forming on the substrate an initiation layer comprising components derived from each of the plurality of initiation precursors. However, the plurality of initiation precursors do not react together as in CVD. Rather, they chemisorb to the substrate, providing a surface onto which a deposition specie may next chemisorb to form a complete layer of desired material.
In the present aspect of the invention, deposition rate is a less significant issue. Accordingly, observation indicates that lower pressures, temperatures, plasma intensities, reactant concentrations, etc., than would otherwise be traditionally accepted may be used to produce a nucleation layer. CVD of a nucleation layer may thus occur at a deposition rate that conventionally might not qualify for a suitable CVD process. For example, traditional CVD of silicon nitride may occur at a temperature between about 600° C. to about 800° C. and a pressure between about 100 milliTorr to about 2 Torr, depending on the selected temperature. If temperature is toward the low end of the range, then pressure is generally toward the high end of the range to stay within the traditional process regime. Exemplary parameters for nontraditional CVD of a nucleation layer may fall below one or both of such ranges or be in the low end of both ranges. Different ranges are conceivable, as determinable by those skilled in the art, depending on deposition precursors, substrate composition, surface properties, and other factors.
Since CVD is typically a non-selective form of deposition, the non-traditional process regime can produce a suitable nucleation layer having a thickness of one atom or molecule or more. Specifically, formation of an approximately 4 to 6 Angstrom silicon nitride nucleation layer from ammonia and dichlorosilane (DCS) has been achieved at a pressure of less than approximately 1.5 Torr, a temperature of approximately 645° C., and a processing time of about 2 minutes. Depending on the CVD technique selected, the same reaction chamber or tool may be used. both for CVD of a nucleation layer and ALD of a deposition layer. Thus, the hybrid structure of the CVD nucleation layer and ALD deposition layer may be formed possessing the advantageous qualities of an ALD material and such formation may be accomplished in situ.
Further, forming a deposition layer may occur by unconventional CVD in a process regime so far outside conventional CVD that the deposition is substantially selective. That is, multiple deposition species may contact the substrate together in the deposition chamber. However, temperature and pressure are low enough that the thickness of the deposition layer over a first part of a substrate is less than 50% of a thickness of the deposition layer over a second part, as shown in FIG. 2. Exemplary parameters include less than about 645° C. and less than about 500 milliTorr or perhaps different ranges, as determinable by those skilled in the art, depending on above mentioned factors. In such a process regime, pressure might bear a more significant effect on selectivity compared to temperature. The unconventional CVD process regime may be conducive to forming a deposition layer only about 1 to 5 atoms or molecules thick. Accordingly, by using a nucleation layer in keeping with the various aspects of the present invention, unconventional CVD may also be used to form a deposition layer.
The first chamber may further comprise any tool suitable for accomplishing techniques such as rapid thermal nitridation (RTN), remote plasma nitridation (RPN), techniques for accomplishing growth of a material (as opposed to deposition) on a substrate, and other techniques. RTN, RPN, and other techniques can involve growth of a nucleation layer non-selectively on first and second surfaces of a substrate. RTN often occurs in an ammonia ambient at a temperature of greater than 700° C. Temperature may be limited to about 800° C. in circumstances where thermal budget limitations exist. RPN is performed similarly except that a plasma is used to provide reactive nitrogen radicals in a manner that provides reduction of process temperature. Accordingly, RPN may be preferred in a circumstance with a sensitive thermal budget.
Examples of process conditions for forming nucleation layers depends on the type of formation process and desired properties of the layer in keeping with the aspect of the invention described above. A silicon nitride nucleation layer may be formed in situ in a low pressure CVD hot wall batch reactor at about 645° C. and about 1.5 Torr. Processing time may be varied to form a layer of a thickness suitable for nucleation. Subsequently, a deposition layer may be formed on the nucleation layer within the low pressure CVD hot wall batch reactor. The deposition layer may be formed by ALD.
Alternatively, a silicon nitride nucleation layer may be formed ex situ using RTN at about 800° C. for about 60 seconds in an ammonia ambient. The substrate and nucleation layer may then be removed to a deposition device suitable for the deposition layer formation, such as by, ALD.
forming a first part of a nucleation layer directly on a first surface of a substrate;
forming a second part of a nucleation layer directly on a second surface of the substrate; and
forming a deposition layer comprising a chemisorbed first specie layer about one monolayer thick directly on the first and second parts of the nucleation layer substantially non-selectively on the first part of the nucleation layer compared to the second part, even though the first and second surfaces of the substrate exhibit a property of the deposition layer forming less readily on the first surface compared to the second surface.
2. The deposition method of claim 1 wherein the forming the first and the second part of the nucleation layer occurs by chemical vapor deposition.
3. The deposition method of claim 2 wherein CVD of the nucleation layer occurs non-selectively at a temperature no greater than about 645° C. and at a pressure of from about 500 milliTorr to about 1.5 Torr.
4. The deposition method of claim 1 wherein the forming the first and the second part of the nucleation layer occurs by atomic layer deposition.
5. The deposition method of claim 4 wherein the atomic layer deposition comprises contacting the substrate with only one precursor specie at a time.
6. The deposition method of claim 4 wherein ALD of the nucleation layer occurs non-selectively at a temperature of from about 400 to about 500° C. and at a pressure of from about 100 milliTorr to about 20 Torr.
7. The deposition method of claim 1 wherein the forming the first and the second part of the nucleation layer occurs simultaneously.
8. The deposition method of claim 1 wherein the forming the first and the second part of the nucleation layer occurs simultaneously and the nucleation layer forms substantially non-selectively on the first surface of the substrate compared to the second surface.
9. The deposition method of claim 1 wherein the forming the deposition layer is performed in situ of the forming the first and the second part of the nucleation layer.
10. The deposition method of claim 1 wherein the second part of the nucleation layer comprises a plurality of components also comprised by the first part.
11. The deposition method of claim 1 wherein the first and the second parts of the nucleation layer comprise silicon nitride, aluminum oxide, or tantalum oxide.
12. The deposition method of claim 1 wherein the first and the second parts of the nucleation layer consist essentially of same components in approximately same proportions.
13. The deposition method of claim 1 wherein a composition of the first part of the nucleation layer differs from a composition of the second part of the nucleation layer.
14. The deposition method of claim 1 wherein the first and the second parts of the nucleation layer comprise silicon nitride and the first part further comprises oxygen.
15. The deposition method of claim 1 wherein a thickness of the nucleation layer comprises less than about 20 Angstroms.
16. The deposition method of claim 15 wherein the thickness comprises less than about 6 Angstroms.
17. The deposition method of claim 1 wherein a thickness of the first part of the nucleation layer is greater than 50% of a thickness of the second part.
18. The deposition method of claim 17 wherein the thickness of the first part is greater than 80% of the thickness of the second part.
19. The deposition method of claim 1 wherein the chemisorbed first specie layer is one monolayer thick.
20. The deposition method of claim 1 wherein the first surface of the substrate exhibits a property of chemisorbing the first specie at a slower rate compared to the second surface.
21. The deposition method of claim 1 wherein the forming the deposition layer further comprises forming a layer at least one monolayer thick of a chemisorbed second specie different from the first specie on the first specie layer.
22. The deposition method of claim 21 wherein the second layer consists essentially of a monolayer.
23. The deposition method of claim 21 wherein the first and second specie layers, in combination, comprise silicon and nitrogen.
24. The deposition method of claim 21 wherein the nucleation layer comprises a material also comprised by the first and second specie layers combined.
25. The deposition method of claim 21 wherein forming the first and second parts of the nucleation layer occurs simultaneously and comprises depositing a complete nucleation layer in a single deposition, the complete nucleation layer and the combined first and second specie layers consisting essentially of same components in approximately same proportions.
26. The deposition method of claim 1 wherein the first and second parts of the nucleation layer comprise aluminum oxide.
27. The deposition method of claim 1 wherein the first and second parts of the nucleation layer comprise tantalum oxide.
28. The deposition method of claim 1 wherein the forming the deposition layer is performed ex situ of the forming the first and the second part of the nucleation layer.
29. A low selectivity deposition method comprising:
simultaneously forming a first part of a nucleation layer on an insulative oxide material and a second part of the nucleation layer on a semiconductive material; and
contacting the nucleation layer with an initiation precursor and forming an initiation layer about one monolayer thick on the first and second parts of the nucleation layer substantially non-selectively on the first part of the nucleation layer compared to the second part.
30. The deposition method of claim 29 wherein the initiation layer is one monolayer thick.
31. The deposition method of claim 29 wherein the first and the second parts of the nucleation layer consist essentially of same components in approximately same proportions.
32. The deposition method of claim 29 wherein the first and the second parts of the nucleation layer comprise silicon nitride and the first part further comprises oxygen.
33. The deposition method of claim 29 wherein a thickness of the nucleation layer comprises less than about 20 Angstroms.
34. The deposition method of claim 29 wherein a thickness of the first part of the nucleation layer is greater than about 50% of a thickness of the second part.
35. The deposition method of claim 29 wherein the insulative oxide exhibits a property of chemisorbing the initiation precursor at a slower rate compared to the semiconductive material.
36. The deposition method of claim 29 further comprising contacting the initiation layer with at least one deposition precursor and forming a deposition layer at least one monolayer thick on the initiation layer.
37. The deposition method of claim 36 wherein the deposition layer consists essentially of a monolayer.
38. The deposition method of claim 36 wherein the deposition precursor consists essentially of a single precursor specie.
39. The deposition method of claim 36 wherein the initiation and deposition layers, in combination, comprise silicon and nitrogen, or tantalum and oxygen, or aluminum and oxygen.
40. The deposition method of claim 36 wherein simultaneously forming the first and second parts of the nucleation layer comprises depositing a complete nucleation layer in a single deposition, the complete nucleation layer and the combined initiation and deposition layers consisting essentially of same components in approximately same proportions.
41. The deposition method of claim 29 wherein simultaneously forming the first and second parts of the nucleation layer comprises non-selective CVD at a temperature no greater than about 645° C. and at a pressure of from about 500 milliTorr to about 1.5 Torr.
42. The deposition method of claim 29 wherein simultaneously forming the first and second parts of the nucleation layer comprises non-selective ALD at a temperature of from about 400 to about 500° C. and at a pressure of from about 100 milliTorr to about 20 Torr.
43. A low selectivity deposition method comprising:
atomic layer depositing a nucleation substance chemisorbed directly on a first surface and a second surface of a substrate substantially non-selectively, wherein the first surface exhibits a property of chemisorbing an atomic layer deposition precursor at a slower rate compared to the second surface and the nucleation substance exhibits a property of chemisorbing the precursor at an approximately equal rate over the first surface compared to over the second surface.
44. The deposition method of claim 43 wherein the nucleation substance comprises an approximately homogeneous composition over the first and the second surface.
45. The deposition method of claim 43 wherein the nucleation layer comprises silicon nitride and a nucleation layer part that is over the first surface further comprises oxygen.
46. The deposition method of claim 43 wherein a thickness of the nucleation layer comprises less than about 20 Angstroms.
47. The deposition method of claim 43 wherein a thickness of a nucleation layer part that is over the first surface is greater than 50% of a thickness a nucleation layer part that is over the second surface.
48. The deposition method of claim 43 wherein ALD of the nucleation substance occures at a temperature of from about 400 to 550° C. and at a pressure of from about 100 milliTorr to about 20 Torr.
49. A low selectivity deposition method comprising:
forming a first part of a nucleation layer directly on a first surface of the substrate in the chamber;
forming a second part of a nucleation layer directly on a second surface of the substrate in the chamber; and
without removing the substrate from the chamber, forming a layer about one monolayer thick of a first chemisorbed precursor directly on the first and second parts of the nucleation layer substantially non-selectively on the first part of the nucleation layer compared to the second part.
50. The deposition method of claim 49 wherein the forming the first and the second part of the nucleation layer occurs simultaneously and the nucleation layer forms substantially non-selectively on the first surface of the substrate compared to the second surface.
51. The deposition method of claim 49 wherein the first surface of the substrate exhibits a property of chemisorbing the first precursor at a slower rate compared to the second surface.
52. The deposition method of claim 49 wherein the first surface comprises borophosphosilicate glass and the second surface comprises polysilicon.
53. A low selectivity deposition method comprising:
placing a substrate in a first chamber;
forming a first part of a nucleation layer directly on a first surface of the substrate in the first chamber;
forming a second part of a nucleation layer directly on a second surface of the substrate in the first chamber;
removing the substrate from the first chamber and placing it in a second chamber different from the first; and
forming a layer of a first chemisorbed specie at least one monolayer thick directly on the first and second parts of the nucleation layer in the second chamber substantially non-selectively on the first part of the nucleation layer compared to the second part.
54. The deposition method of claim 53 wherein the forming the first and the second part of the nucleation layer occurs simultaneously and the nucleation layer forms substantially non-selectively on the first surface of the substrate compared to the second surface.
55. The deposition method of claim 53 wherein the first surface of the substrate exhibits a property of chemisorbing the first specie at a slower rate compared to the second surface.
56. The deposition method of claim 53 wherein the first surface comprises borophosphosilicate glass and the second surface comprises polysilicon.
US09643004 2000-08-21 2000-08-21 Low selectivity deposition methods Active 2021-07-10 US7192888B1 (en)
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US10299140 Expired - Fee Related US6987073B2 (en) 2000-08-21 2002-11-18 Low selectivity deposition methods
US11725740 Abandoned US20070190775A1 (en) 2000-08-21 2007-03-19 Low selectivity deposition methods
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