CN105070784A - New, cheap and efficient CIGS cell absorbent layer preparation process - Google Patents
New, cheap and efficient CIGS cell absorbent layer preparation process Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000002745 absorbent Effects 0.000 title abstract 3
- 239000002250 absorbent Substances 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 104
- 238000004544 sputter deposition Methods 0.000 claims abstract description 40
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 229910052738 indium Inorganic materials 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 18
- 239000011669 selenium Substances 0.000 claims description 37
- 239000011734 sodium Substances 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 22
- 238000005516 engineering process Methods 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 18
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 150000003346 selenoethers Chemical class 0.000 claims description 14
- 229910000058 selane Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 35
- 230000008569 process Effects 0.000 abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 74
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 10
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002196 Pyroceram Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910005543 GaSe Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
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- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003887 surface segregation Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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Abstract
The invention discloses a new, cheap and efficient CIGS cell absorbent layer preparation process (twice two-step method), and provides a technical scheme for solving the dilemma of present CIGS thin-film solar cell industrialization. Through twice sputtering selenylation and alkali metal control, the process can accurately control copper and gallium gradients, shorten whole selenylation time, and improve large-area uniformity; in addition, equipment cost is low. The process comprises: first employing a two-step method to prepare a thicker layer of sodium-free copper-rich CIGS, wherein the sodium-free copper-rich environment substantially promotes the diffusion of indium and gallium, rapidly eliminates the microinhomogeneities of indium and gallium, urges the gallium to diffuse to an upper surface, inhibits the generation of MoSe2, and crystallizes well; the first step has the characteristics of low requirements for selenylation conditions, short selenylation time and high stability, and is suitable for high cycle time and low cost industrialization; and performing cooling and sputtering to prepare a thinner second precast layer (In, Ga)2Se3 containing alkali metal, and performing heating and selenylation for several minutes to complete the preparation of an absorbent layer, wherein the control of alkali metal plays a significant role in controlling conversion efficiency, cycle time, uniformity and stability in the twice two-step method.
Description
Technical field
The present invention relates to the preparation technology of the light absorbing zone of Copper Indium Gallium Selenide (CIGS) thin-film solar cells.
Background technology
Current main flow CIGS absorbed layer preparation technology has three kinds: three stage Co-evaporation method (three-step approach), sputtering and selenization technique method (two step method), sputtering and selenization technique sulfuration method.Simultaneously current CIGS industrialization predicament is difficult to find a suitable technique to solve cost of investment, productive temp, large-area uniformity and stability, battery conversion efficiency problem.
Three steps steam sources of law altogether in U.S.'s regenerative resource laboratory (NREL) preparation technology of the CIGS of efficiency more than 15% that announces in 1994, and evaporation process as shown in Figure 2.In September, 2014, Germany Manz and ZSW realized the conversion efficiency of 21.7%.Three steps steam method basic process altogether: the first step is coevaporation In, Ga, Se element on Mo substrate, form (In, Ga) 2Se3 preformed layer.Second step coevaporation Cu and Se, is obtained by reacting the CIGS thin film of rich Cu with (In, Ga) 2Se3, and in course of reaction, Ga segregation is bottom CIGS, forms the gradient of lower high low Ga.3rd step evaporates a small amount of In, Ga, Se, consume unnecessary CuxSe and obtain the CIGS thin film of surperficial poor copper, this layer forms the gradient of the Ga that upper height bends down, final integral forms the effect of the poor copper of V-shape gradient and surface of a kind of Ga, this is the key of generally acknowledged preparation high efficiency CIGS, as shown in Figure 3.Three steps steam the whole technique of method altogether between 30 ~ 50 minutes, and its overall elemental mole ratios is generally CGI=Cu/ (Ga+In)=0.80 ~ 0.96, GGI=Ga/ (Ga+In)=0.20 ~ 0.36.Film surface quality prepared by three-step approach is good, crystallite dimension is large, surperficial poor copper and there are two gradient band gaps of Ga, be the Perfected process obtaining high efficiency CIGS, current most of laboratory employing coevaporation method can prepare the baby battery efficiency more than 19% on small size.But this method requires the evaporation rate and the evaporation capacity that accurately control four kinds of elements, consistence of composition when being difficult to ensure large area film forming.Process control technology and the longer process time of high equipment cost, the extremely difficulty of three-step approach hinder its bottleneck moving towards market.
Rear selenizing method (two step method) first on substrate the poor copper of sputtering sedimentation one deck have Cu, In, Ga metal initialization layer of sodium, as CuGa In or CuGaIn etc., then in the atmosphere of Se or H2Se, carry out annealing selenizing prepare CIGS absorbed layer, annealing temperature is generally between 500-600 degree.Adopt that good technological temperature in the two step method industrialization in solid-state Se source is 550 ~ 580 degree, annealing time is about 20 ~ 30 minutes.Sputtering method is adopted to prepare metal preformed layer, advantage is that equipment requirement is low, uniformity good, full-automatic continuous seepage, meet heavy industrialization condition, but its shortcoming be cannot as three steps steam method altogether control element gradient, what kind of no matter adopts metal laminated, in selenidation process, Ga all can be deposited on the back electrode portion of CIGS, and surface does not almost have Ga, this causes the Voc of battery lower, and efficiency cannot promote; Two step method is poor copper due to metal preformed layer and mixes sodium, and crystal grain and surface roughness be bad control also.Hypertoxic H2Se during actual industrialization in two step method can be replaced by solid-state Se completely, its mechanism is that solid-state selenium completes selenizing at about 570 degree and only needs thirty or forty to carry out second, the remaining selenizing time is mainly used for Elements Diffusion and grain growth, and this point H2Se is advantage not.The atmosphere evenness of the H2Se generally acknowledged in addition is better than Se steam, but in actual industrialization process, Se steam also has good uniformity in fact.Two step method due to efficiency bottle neck and longer process time, does not almost have enterprise successfully to put goods on the market with two step method volume production CIGS solar cell.
Rear selenizing sulfuration method adds sulfuration process after being the selenization process in two step method.Because two step method surface Ga content is very low, cause surperficial energy gap lower, thus after CIGS generates, then adopt H2S process, the CuInS2 of broad stopband can be formed at film surface, thus also the two gradient-structure of formation improves device open circuit voltage.The shortcoming of this method is the complex process introduced, and sulfuration process overlong time (about 30 minutes), production capacity is low.In state-owned enterprise cost about 1,000,000,000 introduce a set of equipment, but battery efficiency cannot promote for a long time, and production capacity is lower, finally with about 5,000 ten thousand, equipment is sold stopping production.
The present situation of CIGS and predicament
There is a large amount of bankruptcy tides in whole CIGS industry in recent years, and the enterprise that current minority grasps nucleus equipment technology is also only small-scale volume production, and be all at development flexible CIGS battery substantially, to avoid the competition with crystal silicon solar.CIGS industry situation like this is caused to have many reasons:
1. a large amount of company drops into CIGS is before and after 2010, crystal silicon battery price was also higher at that time, but coming years, the cost of crystal-silicon battery slice declines to a great extent, current crystal silicon solar batteries assembly price has been low to moderate 3.3 yuan/watt (2015.4.20), component efficiency is about 16%, and production capacity is superfluous.
2., in main CIGS process, the conversion efficiency of two step method is not high, and production capacity is low; The cost of investment of three-step approach and rear selenizing sulfuration method is higher, and production capacity is low, and CIGS does not have a kind of technology can compete with silicon wafer solar energy in industrialization.
3. when not forming actual market competitiveness; CIGS industrialization is too radical; one side is a large amount of CIGS business failure or has difficulty in taking a step; a company is not had to form the scale production capacity with the market competitiveness; but be high conversion efficiency and the low cost that CIGS industry publicizes CIGS with always carving on the other hand; this doubt directly causing outer bound pair CIGS technology to continue and attack, have a strong impact on investor and judge the investment feasibility of new CIGS technology.The predicament of present CIGS is will in the face of whole production capacity surplus, cost is lower, the crystal silicon solar batteries industry that component efficiency is high, unless there are an exemplary enterprise, squeeze into the market by out and out high production capacity and low price, again could eliminate the misgivings of investor, promote the flourish of CIGS thin film solar cell industry.
At present, CIGS needs a kind of practicable new technology, solves four kinds of problems below simultaneously:
1. high conversion efficiency;
2. the uniformity in large area, stability;
3. low equipment cost, equipment and technology is less demanding;
4. technique beat enough high (cost of investment of unit production capacity).
The present invention is a kind of brand-new CIGS absorbed layer preparation technology, combine two step method and the merits and demerits of three-step approach when industrialization is put into practice, on the basis of two step method low-cost equipment, the selenizing line that extra introducing technical requirement is not high and a sputtered lines, carry out secondary sputtering and selenizing, can accuracy controlling Cu and Ga the same as evaporation gradient in the vertical direction; The omnidistance uniformity using sputtering method to ensure the elemental composition in large area; Make full use of the effect of alkali metal in two step method simultaneously, significantly increase productive temp.This technical process easily realizes in existing laboratory, and the technology in laboratory can be converted into industrial production again, and its all equipment and technology is commercially all very ripe, and the equipment cost of independent development is very low.
Alkali-metal control plays an important role in this 2-2-step technique, introduces Alkali-Metal Na (sodium is represent alkali metal at the CIGS) effect in CIGS technique below:
(1) Na hinders the phase counterdiffusion of In and Ga between CuInSe2 and CuGaSe2, and the phase counterdiffusion of Na to In and Ga plays absolute dominating role.
(2) when there is Na, be in a liquid state under copper-rich phase CuxSe(high temperature) almost no longer affect the phase counterdiffusion of In and Ga; But when there is not Na, the phase counterdiffusion of In and Ga can be promoted.
(3) because the effect of Na, without large than when Na of crystal grain during Na, at rich copper without in the CIGS of sodium, crystal grain can be grown up to 5 microns (transverse directions); Liquid copper-rich phase CuxSe also has significant impact to CIGS grain size, and this is that three steps steam the larger basis of the crystal grain of the standby CIGS of legal system altogether.
(4) Na is mainly present in two interfaces of Mo/CIGS/CdS, there is a small amount of Na element, be in grain boundaries in the inside of CIGS.Na element is not needed, after prepared by CIGS, by Na(or K in CIGS nucleation and growth process) reprocessing is carried out to CIGS surface, equally raise the efficiency; In three steps steaming method altogether, Na is more suitable for adding in the 3rd step.Na, in the copper defect of CIGS spatial induction, plays extremely key effect to the conversion efficiency of CIGS.
(5) Na is in the interface of Mo/CIGS, can promote the growth of MoSe2, and excessive MoSe2 can cause CIGS to come off, and MoSe2 can affect stability during selenizing.
(6) alkali metal K is in the effect of CIGS surface generation, more remarkable than Na (although the mechanism of action is not still come to a conclusion); Since 2014, adopt K to carry out surface treatment to CIGS, significantly improved the conversion efficiency of CIGS battery prepared by three-step approach or two step method.
Summary of the invention
Need the problem solved
Current three-step approach CIGS technique can the graded elemental of accurate control Cu and Ga, and battery conversion efficiency is high, but uniformity controlling is difficult, and equipment cost is high, is not suitable for industrialization promotion; The equipment cost of two step method is low, and uniformity controlling is good, but is difficult to the gradient distribution of control Ga, and battery efficiency is not high, and the selenizing time generally also reaches at about 20 minutes, and production capacity is not high.This new process is based on two step method equipment, take three-steps process as principle, abandon in two step method the way adopting poor copper to have the disposable selenizing of metal preformed layer of sodium, make full use of rich copper and without the advantage of sodium after metal preformed layer during selenizing industrialization, the industrialization for CIGS provides a kind of practicable solution.
Below by the advantage introducing new technology principle in detail and bring.
The technical process of secondary two step method and principle:
1. the process of first time sputtering and first time selenizing: sputter one deck electrode layer Mo on the substrate with Na barrier layer, Mo is prepared with sputtering method the metal preformed layer containing Cu, Ga, In of the rich copper of one deck, and then anneal selenizing Cheng Futong CIGS.The principle of this step is:
(1) graded elemental that this step is formed distributes the first step and second step that are equal in three steps steaming method altogether, and wherein Ga is to the segregation of Mo back electrode, excessive CuxSe upwards surface segregation; The first step in three steps steaming method altogether and second step need the longer time, and large-area uniformity control is more difficult, and equipment cost is high; The time of sputtering method is then shorter, easily control large-area uniformity, and equipment cost is low.
(2) in two step method selenization process, metallic element just completed selenizing in tens seconds and Ga element is all deposited on bottom CIGS, but the existence of Na seriously hinders the phase counterdiffusion of In and Ga between CuInSe2 and CuGaSe2, Ga is reaching in the annealing process of more than 20 minutes the surface being also difficult to be diffused into CIGS.In this technique there is not Alkali-Metal Na in this one deck, and during selenizing, the phase counterdiffusion of Ga and In is significantly accelerated, the Microinhomogeneity that not only disappear fast in the horizontal direction indium metal island and gallium segregation are brought, and makes again abundant Gallium diffusion to upper surface in vertical direction simultaneously.Owing to there is not Na, be in a liquid state under copper-rich phase CuxSe(high temperature phase) also promote between Ga, In element diffusion further; The atomicity of the metallic element of this one deck accounts for the overwhelming majority (the Cu element of 100% and Ga, In element of about 90%) of whole absorbed layer metallic element, and therefore the minimizing of the selenizing time of this one deck is also just equivalent to the minimizing of whole absorbed layer selenizing time;
(3) in two-step process, because CuInSe2, GaGaSe2 are the equilibrium transport in final CIGS, if during selenizing in atmosphere Se content enough, the Se content in CIGS is just very stable.But when actual employing two step method prepares large-area CIGS battery, metal preformed layer must mix Alkali-Metal Na, and Alkali-Metal Na be mainly present in Mo CIGS boundary layer and significantly promote the generation of MoSe2, if the uniformity of selenium atmosphere or temperature is poor, can cause some local MoSe2 undue growth thus cause the inhomogeneities of the Se content of whole CIGS (the under-supply meeting of Se causes very low conversion efficiency), MoSe2 is blocked up will cause the lower even absorbed layer of the fill factor, curve factor of battery directly to drop.In this technique, this step does not add sodium element, and the uniformity of temperature during selenizing, Se atmosphere will reduce greatly to the stability influence of selenizing, and this is to the cost of investment of equipment, and the stability of production is all highly profitable.
(4) the metal preformed layer of two step method is poor copper containing sodium, will crystal grain be caused very little and the roughness on surface is larger during selenizing; And this step is that rich copper is without sodium in this technique, CIGS can be impelled easily to form large grain size, thus reducing temperature fluctuation, selenizing air pressure fluctuation to the impact of CIGS nucleation and growth, the forming core that the crystal grain that this step CIGS is formed is second time selenizing provides good forming core substrate.
Comprehensively, once sputtering with the advantage of a selenization process is: adopt the selenizing equipment compared with low technical requirement and lower cost, complete the selenizing of most metallic element; The selenizing time is shorter, can carry out high-speed production; The large-area uniformity of sputtering method controls very well, and microscopic uniformity is also fine; Selenidation process has good stability; Selenides crystal grain is very large, and surface roughness is less.
2. second time sputters and the process of second time selenizing and principle: on the substrate of above-mentioned rich copper CIGS, below the temperature of 400 degree, again with the lamination of radio frequency sputtering containing the selenides of Ga, In, such as (Ga, In) 2Se3 etc., and containing at least one alkali metal K or Na.The principle of this step is:
(1) this step is equal to the 3rd step in three steps steaming method altogether, and (Ga, In) 2Se3 for consuming the copper-rich phase in the first selenizing layer, and forms the effect of surperficial poor copper; Sputtering method is adopted to replace evaporation, low to the technical requirement of equipment, be also to ensure large-area uniformity;
(2) selenides is ceramic target, and shortcoming is: the poor easy cracking of a. ceramic target heat conduction, therefore ceramic target general thickness is thinner thus cause target consumption too fast, and target is changed frequent, affect productive temp, and target cost is high; B. the radio frequency sputtering power of ceramic target can not be too high, and coating speed is slower;
But the selenides very thin thickness of second time sputtering in this technique, sputtering power and speed do not need very fast, and ceramic target consumption is little, therefore this one deck can adopt ceramic target and radio frequency sputtering can not affect productive temp at a high speed; First time sputtering makes metal selenizing exactly with the final purpose of first time selenizing, and form the gradient of lower high low Ga, can directly adopt sputtering selenides target to replace this process (adopting the ceramic target of different Ga content to form different gradient) in laboratory, but be exactly because these shortcomings of ceramic target are not too applicable to high speed industrialization, in the present invention, adopt rich copper to replace without the metal level selenizing method of sodium;
(3) metal In and CuGa target can produce indium island and gallium segregation when sputtering, and cause microinhomogeneities, and no matter the selenides of sputtering is amorphous state or crystalline state, all has good microscopic uniformity;
(4) metal In and CuGa are not suitable for high temperature sputtering, and selenides target can at high temperature sputter, and when this technique is transformed into industrial production, adopts high temperature sputtering then can save certain energy consumption, and the time of heating up when shortening second time selenizing; Usually in order to improve productive temp, employing is rapidly heated technique (RTP) by first step selenizing, and this step does not then need when industrialization;
(5) although this step heats up after first lowering the temperature again, can bring extra energy consumption, the energy consumption cost only increased is lower than 0.01 yuan/w, and the price comparing crystal silicon battery 3.3 yuan/W almost can be ignored;
The 3rd step time in (6) three steps steaming method is altogether shorter, and after elements vaporization, namely insulation completes the preparation of absorbed layer for about 2 minutes.In this technique, this step is equal to the 3rd step in three steps steaming method altogether, therefore the time of selenizing also only needs a few minutes, although add a selenizing production line, productive temp at a high speed makes actual cost of investment become lower.
Comprehensively, secondary sputtering with the advantage of secondary selenizing is: the selenizing layer of radio frequency sputtering is very thin, is applicable to the high rate of industrialization; Can high temperature substrate be adopted during sputtering, heating-up time during to reduce selenizing, and save certain exhausting and the heating-up time; The Large-Area-Uniform of sputtering easily controls, and the microscopic uniformity of selenides is also fine; The secondary selenizing time is very short, is applicable to the high rate of industrialization.
Concrete solution
Technical scheme of the present invention realizes as follows:
1. on substrate, sputter one deck barrier layer, as SiO2, Al2O3, Si3N4 etc., stop the Na on substrate or other impurity to spread to CIGS absorbed layer;
2. sputter substrate and back electrode that layer of metal Mo, Mo are CIGS;
3. on Mo substrate, sputter one deck containing the first preformed layer of Cu, Ga, In element, element ratio CGI=1.03 ~ 1.3, during the sputtering of the first preformed layer, metal targets composition can be CuGa, In, CuGaIn etc.;
4. the first preformed layer is warmed up to selenizing of once annealing between 520 degree ~ 600 degree, and prepare the first selenizing layer, selenium source can be solid-state Se or H2Se; Selenium source is solid-state Se, and selenizing temperature is preferably 550 ~ 600 degree, and the selenizing time is 2 ~ 10 minutes; Selenium source is H2Se, and selenizing temperature is preferably 520 ~ 580 degree, and the selenizing time is 2 ~ 10 minutes;
5. the first selenides is cooled to less than 400 degree, adopt the selenides of radio frequency sputtering one deck Ga and In and at least comprise a kind of alkali metallic sodium, potassium, obtained second preformed layer, selenides is as (Ga, In) 2Se3, In2Se3, Ga2Se3, (Ga, In) Se, GaSe, InSe, etc., be preferably In2Se3, Ga2Se3 or (Ga, In) 2Se3; Alkali metal can directly mix in selenides, also can adopt sputtering NaF, KF ceramic target; Second preformed layer carries out elemental composition coupling according to the first preformed layer, and make overall element ratio be CGI=0.70 ~ 0.96, GGI=0.2 ~ 0.45, preferred proportion is CGI=0.80 ~ 0.96, GGI=0.25 ~ 0.36;
6. the second preformed layer is warmed up to 550 ~ 600 degree of selenized annealings again, selenium source is solid-state Se or H2Se, and the selenizing time is 3 ~ 10 minutes.
Technical advantage
This technological advantage is low cost of investment and low equipment and technology requirement, productive temp, completely controlled large-area uniformity at a high speed, technology stability, realization and three-step approach just the same Cu, Ga graded elemental distribute and higher battery efficiency again simultaneously, the principle of each step described in detail above and advantage, the technical process of three-step approach and secondary two step method and the contrast of principle are as shown in Figure 4.
Accompanying drawing explanation
Fig. 1 is absorbed layer process chart prepared by secondary two step method.
Fig. 2 is that typical three steps steam legal system altogether for CIGS absorbed layer technique (NREL).
Fig. 3 is the gallium element V word gradient distribution that three steps steam the standby high conversion efficiency CIGS absorbed layer of legal system altogether.
Fig. 4 is the technical process of three-step approach and secondary two step method and the contrast of principle.
Embodiment
Introduce embodiments of the invention below, but the present invention is only limitted to absolutely not this embodiment; CIGS absorbed layer adjustable parameter is extremely many, the constant interval of absorber thickness, elemental composition is larger, if the thickness of CIGS absorbed layer entirety is at 1.0 ~ 3.0 microns, CGI is about 0.80 ~ 0.96, GGI can prepare high efficiency battery about 0.20 ~ 0.45, and the selenization process temperature of general two step method can at about 500 ~ 620 degree, the selenizing time can at about 3 ~ 60 minutes; Alkali-metal detection difficulty is larger, It is generally accepted that alkali doped accounts for about 0.1% of absorbed layer; The thickness of KF or NaF of sputtering is very large at the thickness range of two step method or three-step approach, and can change at about 2 ~ 80nm, general 10 ~ 50nm is appropriate amount; Substrate can adopt simple glass (heatproof about 580 degree), pyroceram (can heatproof more than 600 degree) or flexible metal substrate, is referred to as substrate below; Parameter in the embodiment provided in the present invention is representative value, might not relate to the critical value that experiment is available, and CIGS industry technology personnel can be guided out the embodiment be applicable in a big way easily from embodiment and aforementioned described solution principle.Do not depart from the behavior of rights statement of the present invention, all within protection scope of the present invention.
Embodiment
Substrate sputters the SiOx of one deck about 20 ~ 100nm; When substrate selects simple glass, most high-temperature resistant is 580 degree, and the content of the Na in simple glass is more, generally selects the SiOx of about 50nm; The heatproof of low sodium pyroceram can reach more than 600 degree, selects the SiOx of 20nm then proper; Metal substrate is not containing sodium element, and the effect on barrier layer mainly stops impurity element to spread to CIGS, and different metal substrate selects its barrier layer be applicable to.
SiOx sputters layer of metal Mo, and the back electrode of effect CIGS, the thickness of Mo is advisable with 500 ~ 1000nm.
Mo substrate adopts direct current sputtering Cu75Ga25 (atomic ratio) metal targets, then direct current sputtering metal In target, regulate the thickness of In, make CGI in the scope of 1.03 ~ 1.3 by XRF detection means; In order to reduce metal In island to the impact of final pattern as far as possible, air pressure during splash-proofing sputtering metal In is about 1.5 ~ 2Pa, and substrate should keep lower temperature as far as possible.
First time selenizing is carried out to the first preformed layer; Selenium source can select solid-state Se or H2Se, and pressure selects atmospheric pressure (N2 protection) or vacuum; Suitability for industrialized production should adopt solid-state Se and atmospheric N2 environment; Selenium source adopts solid-state Se, then the temperature of selenium source is at about 320 ~ 500 degree, by nitrogen be transport agent by Se vapor transport to types of flexure, to the first preformed layer selenized annealing at the temperature of 550 ~ 600 degree, be incubated about 2 ~ 10 minutes (not containing the heating and cooling time), obtain the first selenizing layer of rich copper without sodium; Selenium source selects H2Se, then selenizing temperature is 520 ~ 580 to be advisable, about 2 ~ 10 minutes time.
Substrate is cooled to less than 400 degree, the volatilization disappearance of Se easily occurs higher than CIGS when 400 degree; First selenizing layer adopts the (Ga of radio frequency sputtering alkali metal containing, In) 2Se3, can adopt alternating sputtering Ga2Se3 in the lab, the ceramic target such as In2Se3 and KF, NaF, alkali metal gross thickness preferred thickness is about 10nm ~ 50nm, obtains the second preformed layer; In second preformed layer, the mol ratio of Ga and In is generally Ga:In=1:3; Poor layers of copper is formed after Ga2Se3 in second preformed layer, In2Se3 consume the copper-rich phase CuxSe of the first preformed layer on the surface of absorbed layer; Regulate the thickness of the second preformed layer or atomic ratio to make the CGI of overall absorption layer between 0.80 ~ 0.96, GGI is between 0.25 ~ 0.36; The atomic ratio of CuGa target when wherein GGI depends primarily on preparation the first preformed layer, adopts the target of Cu70Ga30 height Ga content that GGI then can be made to reach more than 0.4.
Again substrate is warmed up to 550 ~ 600 degree of annealing selenizings, selenium source adopts solid selenium source or hydrogen selenide, annealing time 3 ~ 10 minutes, complete the preparation of whole CIGS absorbed layer, the absorbed layer average thickness finally obtained is preferably 1.5 ~ 2.5 microns, too thin then absorbing amount reduces and the impact of surface roughness strengthens, and blocked uply then affects target consumption and technique beat, and most preferred thickness is 1.5 ~ 1.8 microns.
Claims (7)
1. a brand-new low-cost high-efficiency CIGS battery obsorbing layer preparation technology, be called for short " secondary two step method ", processing step comprises:
(1) on the substrate with Alkali-barrier layer, with first preformed layer of sputtering method preparation containing the Fu Tongxing of Cu, Ga, In;
(2) once to anneal selenizing to the first preformed layer, generate the first selenizing layer, annealing temperature is 520 ~ 600 degree, and annealing time is 2 ~ 10 minutes;
(3) on the first selenizing layer, comprise Ga, the selenides of In and alkali-metal second preformed layer with sputtering method preparation, alkali metal at least comprises the one in potassium, sodium;
(4) carry out secondary selenized annealing to the second preformed layer and the first selenizing layer, generate battery CIGS absorbed layer, annealing temperature is 550 ~ 600 degree, and annealing time is 3 ~ 10 minutes.
2. the secondary two step method described in claim 1, is characterized in that: the mole elemental ratio Cu/ (Ga+In)=1.03 ~ 1.3 in the first preformed layer.
3. the secondary two step method described in claim 1, is characterized in that: molar ratio Cu/ (Ga+In)=0.8 ~ 0.96, Ga/ (Ga+In)=0.25 ~ 0.36 of overall CIGS absorbed layer.
4. the secondary two step method described in claim 1, is characterized in that: the selenium source of selenizing of once annealing is solid-state selenium, and annealing temperature is 550 ~ 600 degree.
5. the secondary two step method described in claim 1, is characterized in that: the selenium source of selenizing of once annealing is hydrogen selenide, and annealing temperature is 520 ~ 580 degree.
6. the secondary two step method described in claim 1, is characterized in that: underlayer temperature during Slag coating the second preformed layer is below 400 degree.
7. the secondary two step method described in claim 1, is characterized in that: the selenides target as sputter target of the second preformed layer is In2Se3, Ga2Se3 or (In, Ga) 2Se3.
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