IPC분류정보
국가/구분 |
United States(US) Patent
등록
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국제특허분류(IPC7판) |
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출원번호 |
UP-0943658
(2004-09-18)
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등록번호 |
US-7858151
(2011-02-24)
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발명자
/ 주소 |
- Sager, Brian M.
- Roscheisen, Martin R.
- Leidholm, Craig
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출원인 / 주소 |
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인용정보 |
피인용 횟수 :
7 인용 특허 :
33 |
초록
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An absorber layer may be formed on a substrate using atomic layer deposition reactions. An absorber layer containing elements of groups IB, IIIA and VIA may be formed by placing a substrate in a treatment chamber and performing atomic layer deposition of a group IB element and/or one or more group I
An absorber layer may be formed on a substrate using atomic layer deposition reactions. An absorber layer containing elements of groups IB, IIIA and VIA may be formed by placing a substrate in a treatment chamber and performing atomic layer deposition of a group IB element and/or one or more group IIIA elements from separate sources onto a substrate to form a film. A group VIA element is then incorporated into the film and annealed to form the absorber layer. The absorber layer may be greater than about 25 nm thick. The substrate may be coiled into one or more coils in such a way that adjacent turns of the coils do not touch one another. The coiled substrate may be placed in a treatment chamber where substantially an entire surface of the one or more coiled substrates may be treated by an atomic layer deposition process. One or more group IB elements and/or one or more group IIIA elements may be deposited onto the substrate in a stoichiometrically controlled ratio by atomic layer deposition using one or more self limiting reactions.
대표청구항
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What is claimed is: 1. A method for forming an absorber layer containing elements of groups IB, IIIA and VIA, comprising the steps of: atomic monolayer resolution tuning of a bandgap grading of a precursor layer on a substrate, wherein the tuning occurs with spatial uniformity and resolution throug
What is claimed is: 1. A method for forming an absorber layer containing elements of groups IB, IIIA and VIA, comprising the steps of: atomic monolayer resolution tuning of a bandgap grading of a precursor layer on a substrate, wherein the tuning occurs with spatial uniformity and resolution through deposition of at least two types of partial atomic monolayers, one of the types comprises of a different group IB, IIIA, or VIA material relative to a group IB, IIIA, or VIA material in another of the types, with aggregate growth rate directly proportional to a number of reaction cycles rather than the pressure or concentration of precursor gases in the chamber, with control over film thickness, film uniformity, and conformality; processing the substrate in a roll-to-roll process by using an elongate treatment chamber; wherein processing includes annealing the substrate with a precursor layer-thereon in one or more steps; wherein the deposition of partial atomic monolayers comprises: exposing a target surface of the substrate to a group IB, IIIA, or VIA precursor agent and then a reducing agent, wherein deposited atoms occupy only a portion of all deposition sites on the target surface; repeating the deposition of partial atomic monolayers using same or different group IB, IIIA, or VIA precursor agents and reducing agents until a desired atomically-graded deposition profile of at least two materials from the group consisting of group IB, IIIA, and VIA is formed in the precursor layer. 2. The method of claim 1 wherein the absorber layer is between about 25 nm and about 5000 nm thick. 3. The method of claim 1 wherein the absorber layer is between about 25 nm and about 3000 nm thick. 4. The method of claim 1 wherein the absorber layer is between about 100 nm and about 2000 nm thick. 5. The method of claim 1 wherein the absorber layer is between about 500 nm and about 2000 nm thick. 6. The method of claim 1 wherein the absorber layer is between about 1000 nm and about 2000 nm thick. 7. The method of claim 1 wherein the substrate is coiled in the treatment chamber. 8. The method of claim 7 wherein the precursor layer is formed by atomic layer deposition carried out in a stoichiometrically controlled ratio using one or more self-limiting reactions involving precursor gases of the group IB and group IIIA elements in a mix ratio that translates into a deposition ratio of the group IB and IIIA elements on the substrate, and/or by an atomic layer deposition sequence involving two or more self-limiting single species deposition reactions with precursor gases of the group IB and group IIIA elements; and incorporating an element of group VIA into the absorber layer. 9. The method of claim 7 wherein the element of group VIA is selenium or sulfur. 10. The method of claim 7 wherein incorporating the element of group VIA into the absorber layer includes exposing the film to selenium vapor, sulfur vapor, H2Se, H2S, one or more other selenium- or sulfur-containing compounds, or combinations or mixtures of two or more of these. 11. The method of claim 7 wherein incorporating the element of group VIA into the absorber layer involves using one or more precursor gases containing one or more elements of group VIA. 12. The method of claim 11 wherein the element of group VIA is incorporated into the absorber film through a sequence of atomic layer deposition steps. 13. The method of claim 11 wherein the sequence of atomic layer deposition steps includes the use of one or more metal organic precursors containing selenium, sulfur, H2Se, H2S, one or more other selenium- or sulfur-containing compounds, or combinations or mixtures of two or more of these. 14. The method of claim 13 wherein the one or more metal organic precursors containing selenium or sulfur include dimethyl selenide, dimethyl diselenide, or diethyl diselenide. 15. The method of claim 14 wherein incorporating the element of group VIA takes place either on a monolayer by monolayer basis, or periodically, with an exposure period substantially longer than a monolayer deposition cycle, or at the end of an absorber layer deposition sequence. 16. The method of claim 1 wherein performing atomic layer deposition includes exposing the substrate to one or more precursors of copper, indium, and/or gallium, and/or aluminum, and/or selenium, and/or sulfur. 17. The method of claim 16 wherein the precursors include one or more Cu(I) compounds, one or more Cu(II) compounds, CuCl, copper iodide, or other copper halides, one or more copper diketonates, Cu(II)-2,2,6,6,-tetramethyl-3,5,-heptanedionate (Cu(thd)2)), Cu (II) 2,4-pentanedionate, Cu(II) hexafluoroacetylacetonate (Cu(hfac)2), Cu(II) acetylacetonate (Cu(acac)2), Cu(II) dimethylaminoethoxide, one or more copper ketoesters, one or more organocopper precursors containing Si or Ge, one or more other organocopper precursors and combinations or mixtures of the above, indium chloride, indium iodide, one or more other indium halides, dimethylindium chloride, trimethylindium, indium 2,4-pentanedionate (indium acetylacetonate), indium hexafluoropentanedionate, indium methoxyethoxide, indium methly(trimethylacetyl)acetate, indium trifluoropentanedionate, one or more organoindium precursors containing Si or Ge, one or more other organoindium precursors, and combinations or mixtures of the above, diethylgallium chloride, gallium triiodide, one or more other gallium halides, Ga (III) 2,4-pentanedionate, Ga (III) ethoxide, Ga(III) 2,2,6,6,-tetramethylheptanedionate, tris(dimethylaminogallium), gallium (I) salts, gallium chloride, gallium fluoride, gallium iodide, gallium acetate, other gallium (I)-based organometallic precursors, one or more organogallium precursors containing Si or Ge, one or more other organogallium precursors and combinations or mixtures of the above, aluminum chloride, aluminum iodide, or other halides, dimethylaluminum chloride, one or more aluminum butoxides, aluminum di-s-butoxide ethylacetoacetate, aluminum diisopropoxide ethylacetoacetate, aluminum ethoxide, aluminum isopropoxide, aluminum hexafluoropentanedionate, Al(III) 2,4,-pentanedionate, AI(III) 2,2,6,6-tetramethyl3,5-heptanedionat-e, aluminum trifluoroacetate, trisisobutylaluminum, aluminum silicate, one or more organoaluminum or organometallic precursors containing Si or Ge, one or more other organoaluminum or other organometallic precursors and combinations or mixtures of the above. 18. The method of claim 16 further comprising, after exposing the substrate to-one or more organometallic precursors of copper, indium, and/or gallium, and/or aluminum, and/or selenium, and/or sulfur, exposing the substrate to one or more reducing agents or proton-donor compounds. 19. The method of claim 18 wherein the one or more reducing agents or proton donor compounds include water (H2O), hydrogen peroxide (H2O2), methanol, ethanol, isopropyl alcohol, one or more butyl alcohols, one or more other alcohols, carbon monoxide (CO), Oxygen gas (O2), formalin, or combinations or mixtures of two or more of these. 20. The method of claim 1 wherein the precursor layer is formed by performing atomic layer deposition of one or more group IB elements and one or more group IIIA elements and includes an atomic layer deposition sequence involving two or more self-limiting single species deposition reactions with precursor gases of the group IB and group IIIA elements and varying the sequence of exposure pulses of the precursor gases. 21. The method of claim 1 wherein the precursor layer is formed by performing atomic layer deposition of the group IB and group IIIA elements and includes varying the concentration of the group IB and group IIIA elements in the absorber layer as a function of depth. 22. The method of claim 21 wherein performing atomic layer deposition of one or more group IB elements and one or more group IIIA elements includes an atomic layer deposition sequence involving two or more self-limiting single species deposition reactions with precursor gases of the group IB and group IIIA elements and varying a duration of exposure of the substrate to the precursor gases or varying the sequence of deposition reactions to vary the concentration of the group IB and group IIIA elements in the absorber layer as a function of depth. 23. The method of claim 21 wherein the sequence of deposition reactions produces a concentration of the one or more group IIIA elements that is relatively higher at and near a front region and a back region of the absorber layer, and relatively lower in a central region of the absorber layer, resulting in a “saddle” profile for the concentration of the one or more group IIIA elements as a function of depth within the absorber layer. 24. The method of claim 23 wherein the one or more group IIIA elements includes gallium (Ga) and/or Indium. 25. The method of claim 24 wherein the sequence of deposition reactions produces a Ga concentration that is relatively low at or near a back region and a central region of the absorber layer but higher at a front end, while an Indium concentration is highest in the central region of the absorber layer and lesser at both the back region and front region. 26. The method of claim 25 wherein the one or more group IB elements have a relatively higher concentration at and near the back of the absorber layer and in a relatively lesser concentration in the central and front regions of the absorber layer. 27. The method of claim 26 wherein the one or more group IB elements includes copper (Cu). 28. The method of claim 27 wherein performing atomic layer deposition of one or more group IB elements and/or one or more group IIIA elements onto the substrate includes depositing gallium by atomic vapor deposition. 29. The method of claim 1 wherein the precursor layer is formed by performing atomic layer deposition of one or more group IB elements and one or more group IIIA elements, wherein the atomic layer deposition uses a precursor gas of group IB and a precursor gas of group IIIA that do not react with each other in the gas phase during deposition. 30. The method of claim 1 wherein the precursor layer is formed by performing atomic layer deposition and includes the use of one or more precursor gases from the group of halides of copper, indium and/or gallium. 31. The method of claim 1 wherein the substrate is at least 2 m wide. 32. The method of claim 1 wherein the substrate comprises of a material selected from the group consisting of: metal foil, aluminum, alloy foil, titanium, a polymer, a polyimide, polyetheretherketone (PEEK), polyethersulfone (PES), polyetherimide (PEI), polyethylene naphthalate (PEN), Polyester (PET), and a metallized plastic. 33. The method of claim 1, further comprising incorporating an element of group VIA into the absorber layer before and/or during flash heating of the absorber layer. 34. The method of claim 33 wherein flash heating the absorber layer includes heating the absorber layer to an average plateau temperature of between about 200° C. and about 600° C. 35. The method of claim 33 wherein the flash heating lasts between about 2 minutes and about 10 minutes. 36. The method of claim 1, further comprising the step of depositing an electrode layer on the substrate by atomic layer deposition before depositing the group IB, and/or group IIIA elements. 37. The method of claim 36 wherein the electrode layer includes molybdenum. 38. The method of claim 37 wherein depositing the electrode includes the use of one or more precursors from the group of molybdenum chloride, molybdenum iodide, other halides of molybdenum, MoCl5, molybdenum ethoxide, molybdenum VI oxide bis(2,4-pentandedionate), molybdenum hexacarbonyl, molybdenum disilicide, organomolybdenum precursors containing Si or Ge, other organomolybdenum precursors and combinations or mixtures of the above. 39. The method of claim 36 further comprising the step of forming an adhesion layer between the substrate and the electrode layer. 40. The method of claim 39 wherein forming the adhesion layer includes, before depositing the electrode layer, depositing a layer of vanadium, chromium, tungsten or silicon dioxide on the substrate. 41. The method of claim 40 wherein depositing the layer of vanadium, chromium, tungsten or silicon dioxide includes atomic layer deposition using one or more precursors from the group consisting of: tungsten chlorides, other halides, tungsten ethoxide, tungsten silicide, organotungsten precursors containing Si or Ge, other organotungsten precursors and combinations or mixtures of the above, vanadium chloride, vanadium iodide, other vanadium halides, vanadium tri-n-propoxide oxide, vanadium triisopropoxide oxide, vanadium trisisobutoxide, vanadium III 2,4-pentanedionate, vanadium IV oxide bis(2,4-pentanedionate), vanadium IV oxide bis(hexafluoropentanedionate), vanadium IV oxide bis(benzoylacetonate), organovanadium precursors containing Si or Ge, other organovanadium precursors and combinations or mixtures of the above, chromium chloride, chromium iodide, other chromium halides, chromium III benzoylacetonate, chromium (III) hexafluoropentanedionate, chromium III isopropoxide, chromium III 2,4-pentanedionate, chromium III 2,2,6,6-tetramethylheptanedionate, chromium III trifluoropentanedionate, chromium II acetate, chromium III acetate, chromium III 2-ethylheaxonate, organochromium precursors containing Si or Ge, other organochromium precursors and combinations or mixtures of the above, organometallic precursors containing Si or Ge, other organometallic precursors, other halides and combinations or mixtures of the above. 42. The method of claim 36 further comprising, depositing a window layer on the absorber layer. 43. The method of claim 42 wherein the window layer includes Cadmium Sulfide (CdS). 44. The method of claim 43 wherein depositing the window layer includes the use of one or more precursors selected from the group of consisting of: cadmium chloride, cadmium iodide, other halides, cadmium 2,4-pentanedionate, cadmium acetate, cadmium formate, dimethylcadmium, organocadmium precursors containing Si or Ge, other organocadmium precursors, organometallic precursors containing Si or Ge, other organometallic precursors and combinations or mixtures of the above. 45. The method of claim 43 wherein depositing the window layer on the absorber layer includes depositing the window layer and the absorber layer in the same chamber without removing the substrate between depositions. 46. The method of claim 45 wherein the window layer is deposited by atomic layer deposition, chemical surface deposition or liquid-based atomic layer epitaxy. 47. The method of claim 46, further comprising depositing a transparent electrode layer on the window layer by atomic layer deposition in the same chamber without removing the substrate between depositions. 48. The method of claim 47 wherein the transparent electrode layer includes Zinc Oxide (ZnO). 49. The method of claim 48 wherein depositing the transparent electrode includes the use of one or more precursors selected from the group consisting of: zinc chloride, zinc iodide, other zinc halides, dimethyl zinc, diethyl zinc, zinc N,N-dimethylaminoethoxide, zinc methoxyethoxide, zinc 2,4-pentanedionate, zinc 2,2,6,6-tetramethyl-3,5-heptanedionate, zinc acetate, zinc bis(hexamethyldisilazide), and organozinc or organometallic precursors containing Si or Ge, other organozinc or organometallic precursors and combinations or mixtures of the above. 50. A method for forming an absorber layer containing elements of groups IB, IIIA and VIA, comprising the steps of: performing atomic layer deposition of a group IB element from a first source and a first group IIIA element from a second source and a second group IIIA element from a third source onto a substrate to form a film; atomic monolayer resolution tuning of a bandgap grading of the precursor layer on a substrate, wherein the tuning occurs with spatial uniformity and resolution through deposition of at least two types of partial atomic monolayers, one of the types comprises of a different group IB, IIIA, or VIA material relative to a group IB, IIIA, or VIA material in another of the types, from each of the first source, the second source, and the third source, with aggregate growth rate directly proportional to a number of reaction cycles rather than the pressure or concentration of precursor gases in the chamber, with control over film thickness, film uniformity, and conformality; wherein the deposition of partial atomic monolayers comprises: exposing a target surface of the substrate to a group IB, IIIA, or VIA precursor agent and then a reducing agent, wherein deposited atoms occupy only a portion of all deposition sites on the target surface; repeating the deposition of partial atomic monolayers using same or different group IB, IIIA, or VIA precursor agents and reducing agents until a desired atomically-graded deposition profile of at least two materials from the group consisting of group IB, IIIA, and VIA is formed in the precursor layer formed in the film; annealing the film using rapid thermal processing comprising heating at a rate between about 5° C./sec and about 15° C./sec until a desired temperature is reached in a non-VIA environment to form an annealed film; and incorporating one or more group VIA elements into the annealed film to form the absorber layer. 51. The method of claim 50 wherein the absorber layer is between about 1 nm and about 5000 nm thick. 52. The method of claim 50 wherein the group VIA element is sulfur or selenium. 53. The method of claim 50 wherein incorporating an element of group VIA into the absorber layer is performed by exposing the film to selenium vapor, sulfur vapor, H2Se or H2S one or more other selenium- or sulfur-containing compounds, or combinations or mixtures of two or more of these. 54. The method of claim 50 wherein performing atomic layer deposition of one or more group IB elements and one or more group IIIA elements includes varying the concentration of the group IB and group IIIA elements in the absorber layer as a function of depth. 55. The method of claim 54 wherein performing atomic layer deposition of one or more group IB elements and one or more group IIIA elements includes an atomic layer deposition sequence involving two or more self-limiting single species deposition reactions with precursor gases of the group IB and group IIIA elements and varying a duration of exposure of the substrate to the precursor gases or varying the sequence of deposition reactions to vary the concentration of the group IB and group IIIA elements in the absorber layer as a function of depth. 56. The method of claim 54 wherein the sequence of deposition reactions produces a concentration of the one or more group IIIA elements that is relatively higher at and near a front region and a back region of the absorber layer, and relatively lower in a central region of the absorber layer, resulting in a “saddle” profile for the concentration of the one or more group IIIA elements as a function of depth within the absorber layer.
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