Source: http://www.google.com/patents/US8012442?dq=system+for+measuring+web+traffic&ei=Lg8FT__TIIr-sQKzxaGRCg
Timestamp: 2015-06-02 04:22:17
Document Index: 744126721

Matched Legal Cases: ['Application No. 07', 'Application No. 07', 'Application No. 200780020120', 'Application No. 200780020120', 'Application No. 096110730', 'Application No. 096110747', 'Application No. 096110749']

Patent US8012442 - Method of forming mixed rare earth nitride and aluminum nitride films by ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA method is provided for depositing a gate dielectric that includes at least two rare earth metal elements in the form of a nitride or an aluminum nitride. The method includes disposing a substrate in a process chamber and exposing the substrate to a gas pulse containing a first rare earth precursor...http://www.google.com/patents/US8012442?utm_source=gb-gplus-sharePatent US8012442 - Method of forming mixed rare earth nitride and aluminum nitride films by atomic layer depositionAdvanced Patent SearchPublication numberUS8012442 B2Publication typeGrantApplication numberUS 11/278,393Publication dateSep 6, 2011Filing dateMar 31, 2006Priority dateMar 31, 2006Fee statusPaidAlso published asUS20070237698, US20110165328, WO2007118006A2, WO2007118006A3Publication number11278393, 278393, US 8012442 B2, US 8012442B2, US-B2-8012442, US8012442 B2, US8012442B2InventorsRobert D. ClarkOriginal AssigneeTokyo Electron LimitedExport CitationBiBTeX, EndNote, RefManPatent Citations (43), Non-Patent Citations (64), Classifications (13), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetMethod of forming mixed rare earth nitride and aluminum nitride films by atomic layer deposition
US 8012442 B2Abstract
A method is provided for depositing a gate dielectric that includes at least two rare earth metal elements in the form of a nitride or an aluminum nitride. The method includes disposing a substrate in a process chamber and exposing the substrate to a gas pulse containing a first rare earth precursor and to a gas pulse containing a second rare earth precursor. The substrate may also optionally be exposed to a gas pulse containing an aluminum precursor. Sequentially after each precursor gas pulse, the substrate is exposed to a gas pulse of a nitrogen-containing gas. In alternative embodiments, the first and second rare earth precursors may be pulsed together, and either or both may be pulsed together with the aluminum precursor. The first and second rare earth precursors comprise a different rare earth metal element. The sequential exposing steps may be repeated to deposit a mixed rare earth nitride or aluminum nitride layer with a desired thickness. Purge or evacuation steps may also be performed after each gas pulse.
1. A method for forming a mixed rare earth nitride or a mixed rare earth aluminum nitride film, comprising:
exposing the substrate to a gas pulse sequence to deposit a mixed rare earth nitride film or a mixed rare earth aluminum nitride film with a desired thickness, wherein the gas pulse sequence includes, in any order:
a) sequentially first, exposing the substrate to a gas pulse comprising a first rare earth precursor, and second, exposing the substrate to a gas pulse comprising a nitrogen-containing gas;
b) sequentially first, exposing the substrate to a gas pulse comprising a second rare earth precursor, and second, exposing the substrate to a gas pulse comprising the nitrogen-containing gas, wherein the first and second rare earth precursors contain different rare earth metal elements of differing and mismatched atomic sizes; and
c) optionally, sequentially first, exposing the substrate to a gas pulse containing an aluminum precursor and second, exposing the substrate to a gas pulse containing the nitrogen-containing gas,
wherein each of a), b) and optionally c) are optionally repeated any number of desired times, wherein the gas pulse sequence including a), b) and optionally c) is optionally repeated, in any order, any number of desired times to achieve the desired thickness, and wherein the different rare earth metal elements are in solid solution in the mixed rare earth nitride or the mixed rare earth aluminum nitride film and wherein the mixed rare earth nitride or the mixed rare earth aluminum nitride film has a dielectric constant that is greater than the dielectric constant of a nitride or an aluminum nitride film having only one of the different rare earth metal elements present in the mixed rare earth nitride or the mixed rare earth aluminum nitride film.
3. The method of claim 1, wherein the nitrogen-containing gas comprises NH3, N2H4, or plasma excited nitrogen, or a combination thereof.
performing one or more additional exposure steps, wherein each additional exposure step comprises sequentially first, exposing the substrate to a gas pulse comprising an additional rare earth precursor, and second, exposing the substrate to a gas pulse comprising the nitrogen-containing gas, wherein each additional rare earth precursor contains a different rare earth metal element than the rare earth metal elements in the first and second rare earth precursors.
10. The method of claim 1, wherein the mixed rare earth nitride or the mixed rare earth aluminum nitride film has a thickness between about 5 and about 200 angstroms.
11. The method of claim 1, wherein the first exposing steps in a) and b) are performed concurrently and the second exposing steps in a) and b) are performed concurrently, whereby to sequentially first expose the substrate to a gas pulse comprising both the first and second rare earth precursors, and second expose the substrate to a gas pulse comprising the nitrogen-containing gas.
12. A method for forming a mixed rare earth nitride film, comprising:
c) exposing the substrate to a gas pulse of an nitrogen-containing gas; and
d) repeating steps b) and c) a desired number of times to deposit a mixed rare earth nitride film with a desired thickness, wherein the at least two different rare earth metal elements are of differing and mismatched atomic size and are in solid solution in the mixed rare earth nitride film and wherein the mixed rare earth nitride film has a dielectric constant that is greater than the dielectric constant of a nitride film having only one of the different rare earth metal elements present in the mixed rare earth nitride film.
14. The method of claim 12, wherein the nitrogen-containing gas comprises NH3, N2H4, or plasma excited nitrogen, or a combination thereof.
16. The method of claim 12, wherein the mixed rare earth nitride film has a thickness between about 5 and about 200 angstrom.
17. A method for forming a mixed rare earth aluminum nitride film, comprising:
b) sequentially first, exposing the substrate to a gas pulse comprising a plurality of rare earth precursors containing at least two different rare earth metal elements, and second, exposing the substrate to a gas pulse of an nitrogen-containing gas;
c) sequentially first, exposing the substrate to a gas pulse containing an aluminum precursor and second, exposing the substrate to a gas pulse containing an nitrogen-containing gas; and
d) repeating steps b)-c) a desired number of times to deposit a mixed rare earth aluminum nitride film with a desired thickness, wherein the at least two different rare earth metal elements are of differing and mismatched atomic size and are in solid solution in the mixed rare earth aluminum nitride film and wherein the mixed rare earth aluminum nitride film has a dielectric constant that is greater than the dielectric constant of an aluminum nitride film having only one of the different rare earth metal elements present in the mixed aluminum nitride film.
19. The method of claim 17, wherein the nitrogen-containing gas comprises NH3, N2H4, or plasma excited nitrogen, or a combination thereof.
22. A method for forming a mixed rare earth aluminum nitride film, comprising:
c) exposing the substrate to a gas pulse of a nitrogen-containing gas;
d) repeating steps b)-c) a desired number of times to deposit a mixed rare earth aluminum nitride film with a desired thickness, wherein the at least two different rare earth metal elements are of differing and mismatched atomic size and are in solid solution in the mixed rare earth aluminum nitride film and wherein the mixed rare earth aluminum nitride film has a dielectric constant that is greater than the dielectric constant of an aluminum nitride film having only one of the different rare earth metal elements present in the mixed rare earth aluminum nitride film.
24. The method of claim 22, wherein the nitrogen-containing gas comprises NH3, N2H4, or plasma excited nitrogen, or a combination thereof.
This application is related to co-pending U.S. patent application Ser. No. 11/278,387, entitled “METHOD OF FORMING MIXED RARE EARTH OXIDE AND ALUMINATE FILMS BY ATOMIC LAYER DEPOSITION,” filed on even date herewith; co-pending U.S. patent application Ser. No. 11/278,393, entitled “METHOD OF FORMING MIXED RARE EARTH OXYNITRIDE AND ALUMINUM OXYNITRIDE FILMS BY ATOMIC LAYER DEPOSITION,” filed on even date herewith; co-pending U.S. patent application Ser. No. 11/278,397, entitled “SEMICONDUCTOR DEVICE WITH GATE DIELECTRIC CONTAINING MIXED RARE EARTH ELEMENTS,” filed on even date herewith; and co-pending U.S. patent application Ser. No. 11/278,399, entitled “SEMICONDUCTOR DEVICE WITH GATE DIELECTRIC CONTAINING ALUMINUM AND MIXED RARE EARTH ELEMENTS,” filed on even date herewith. The entire contents of these applications are herein incorporated by reference in their entirety.
The present invention relates to a method of forming dielectric materials for semiconductor manufacturing, and more particularly to a method of forming high dielectric constant mixed rare earth nitride and aluminum nitride films containing a plurality of different rare earth metal elements.
Embodiments of the invention provide a method for depositing mixed rare earth nitride and aluminum nitride films by ALD and plasma enhanced ALD (PEALD). The mixed rare earth nitride and aluminum nitride films contain a mixture of a plurality of different rare earth metal elements, including Y, Lu, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. For example, the mixed rare earth nitride and aluminum nitride films may be used in advanced semiconductor applications that include future generations of high-k dielectric materials for use as both capacitor and gate dielectrics.
According to one embodiment of the invention, a method is provided for forming a mixed rare earth nitride film or a mixed rare earth aluminum nitride film by disposing a substrate in a process chamber, and exposing the substrate to a gas pulse sequence to deposit a mixed rare earth nitride film or a mixed rare earth aluminum nitride film with a desired thickness. The gas pulse sequence includes, in any order: a) sequentially first, exposing the substrate to a gas pulse containing a first rare earth precursor, and second, exposing the substrate to a gas pulse containing an nitrogen-containing gas; b) sequentially first, exposing the substrate to a gas pulse containing a second rare earth precursor, and second, exposing the substrate to a gas pulse containing an nitrogen-containing gas, where the first and second rare earth precursors each contain a different rare earth metal element; and optionally, c) sequentially first, exposing the substrate to a gas pulse containing an aluminum precursor and second, exposing the substrate to a gas pulse containing the nitrogen-containing gas. The method further includes each of a), b) and optionally c) being optionally repeated any number of desired times, and the gas pulse sequence including a), b) and optionally c) being optionally repeated, in any order, any number of desired times to achieve the desired thickness. According to one embodiment of the invention, the method further includes purging or evacuating the process chamber after at least one of the exposing steps.
According to another embodiment of the invention, a method is provided for forming a mixed rare earth nitride film by a) disposing a substrate in a process chamber, b) sequentially exposing the substrate to a gas pulse comprising a plurality of rare earth precursors each containing a different rare earth metal element, c) exposing the substrate to a pulse containing a nitrogen-containing gas, and d) repeating steps b) and c) a desired number of times to deposit a mixed rare earth nitride film with a desired thickness. According to one embodiment of the invention, the method further includes purging or evacuating the process chamber after at least one of the exposing steps. According to another embodiment of the invention, the gas pulse of step b) includes an aluminum precursor, whereby a mixed rare earth aluminum nitride film is formed. According to an alternate embodiment, after steps b) and c) are performed, the substrate is exposed to another pulse sequence including exposure to an aluminum precursor followed by exposure to a nitrogen-containing gas, whereby a mixed rare earth aluminum nitride film is formed.
Examples of L group alkoxides include tert-butoxide, iso-propoxide, ethoxide, 1-methoxy-2,2-dimethyl-2-propionate (mmp), 1-dimethylamino-2,2′-dimethyl-propionate, amyloxide, and neo-pentoxide. Examples of halides include fluoride, chloride, iodide, and bromide. Examples of aryloxides include phenoxide and 2,4,6-trimethylphenoxide. Examples of amides include bis(trimethylsilyl)amide, di-tert-butylamide, and 2,2,6,6-tetramethylpiperidide (TMPD). Examples of cyclopentadienyls include cyclopentadienyl, 1-methylcyclopentadienyl, 1,2,3,4-tetramethylcyclopentadienyl, 1-ethylcyclopentadienyl, pentamethylcyclopentadienyl, 1-iso-propylcyclopentadienyl, 1-n-propylcyclopentadienyl, and 1-n-butylcyclopentadienyl. Examples of alkyls include bis(trimethylsilyl)methyl, tris(trimethylsilyl)methyl, and trimethylsilylmethyl. An example of a silyl is trimethylsilyl.
Examples of amidinates include N,N′-di-tert-butylacetamidinate, N,N′-di-iso-propylacetamidinate, N,N′-di-isopropyl-2-tert-butylamidinate, and N,N′-di-tert-butyl-2-tert-butylamidinate. Examples of β-diketonates include 2,2,6,6-tetramethyl-3,5-heptanedionate (THD), hexafluoro-2,4-pentandionate, and 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate (FOD). An example of a ketoiminate is 2-iso-propylimino-4-pentanonate. Examples of silanoates include tri-tert-butylsiloxide and triethylsiloxide. An example of a carboxylate is 2-ethylhexanoate.
Lu precursors: Lu(N(SiMe3)2)3, ((iPr)Cp)3Lu, Cp3Lu, Lu(THD)3, Lu[OOCCH(C2H5)C4H9]3, Lu(O(iPr))3, and Lu(acac)3 In the above precursors, as well as precursors set forth below, the following common abbreviations are used: Si: silicon; Me: methyl; Et: ethyl; iPr: isopropyl; nPr: n-propyl; Bu: butyl; nBu: n-butyl; sBu: sec-butyl; iBu: iso-butyl; tBu: tert-butyl; Cp: cyclopentadienyl; THD: 2,2,6,6-tetramethyl-3,5-heptanedionate; TMPD: 2,2,6,6-tetramethylpiperidide; acac: acetylacetonate; hfac: hexafluoroacetylacetonate; and FOD: 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate.
Mixed Rare Earth Nitrides: LaxLuyNa, YxLuyNa, YxLayNa, NdxLayNa, and LaxPryNa.
Mixed Rare Earth Oxynitrides: LaxLuyOmNn, YxLuyOmNa, YxLayOmNn, NdxLayOmNn, and LaxPryOmNn.
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Matter 12 (2000) 3113-3118.64Zhao et al., Ternary Rare-Earth Metal Oxide High-k Layers on Silicon Oxide, Applied Physics Letters 86, 132903 (2005.Classifications U.S. Classification423/263, 427/255.19International ClassificationC01F17/00Cooperative ClassificationC23C16/34, H01L21/318, C23C16/45525, H01L21/3142, C23C16/45531European ClassificationH01L21/314A2, H01L21/318, C23C16/455F2B4, C23C16/455F2, C23C16/34Legal EventsDateCodeEventDescriptionFeb 18, 2015FPAYFee paymentYear of fee payment: 4May 18, 2006ASAssignmentOwner name: TOKYO ELECTRON LIMITED, JAPANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CLARK, ROBERT D.;REEL/FRAME:017637/0466Effective date: 20060406RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services