CN106409659A - Compound semiconductor film and preparation method thereof - Google Patents
Compound semiconductor film and preparation method thereof Download PDFInfo
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- CN106409659A CN106409659A CN201610890513.3A CN201610890513A CN106409659A CN 106409659 A CN106409659 A CN 106409659A CN 201610890513 A CN201610890513 A CN 201610890513A CN 106409659 A CN106409659 A CN 106409659A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000004065 semiconductor Substances 0.000 title claims abstract description 41
- 239000011669 selenium Substances 0.000 claims abstract description 154
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 136
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000000758 substrate Substances 0.000 claims abstract description 101
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract 2
- 239000010408 film Substances 0.000 claims description 143
- 239000010409 thin film Substances 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 33
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 33
- 238000005987 sulfurization reaction Methods 0.000 claims description 31
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 30
- 229910052733 gallium Inorganic materials 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229910052738 indium Inorganic materials 0.000 claims description 17
- 239000005864 Sulphur Substances 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 85
- 238000000034 method Methods 0.000 abstract description 39
- 230000008569 process Effects 0.000 abstract description 29
- 238000004073 vulcanization Methods 0.000 abstract description 20
- 239000000376 reactant Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 2
- 210000001142 back Anatomy 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000003346 selenoethers Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 230000002860 competitive effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 229910005543 GaSe Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910000058 selane Inorganic materials 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000036186 satiety Effects 0.000 description 1
- 235000019627 satiety Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052959 stibnite Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a compound semiconductor film and a preparation method thereof. The preparation method of the compound semiconductor film comprises the following steps of providing substrates, wherein each substrate comprises a base, a metal film preformed layer and a solid selenium film which are stacked in sequence; arranging two substrates at an interval in parallel and making the selenium films in the two substrates opposite; and simultaneously carrying out selenylation and vulcanization on the metal film preformed layers under the atmosphere containing a gaseous sulfur source, and obtaining the compound semiconductor film on the substrates. The two substrates which are arranged at the interval in parallel are taken as confinement boundaries to form a confinement reaction space, when selenylation and vulcanization are simultaneously carried out, reactants and volatile phases in a high-temperature processing process are confined in the space, so that the out-of-control influence of the reactant loss on a reaction process is avoided, a competing reaction relation between selenium and sulfur, which is difficult to control from microcosmic perspective, can be transferred to a macroscopic space which is easier to implement to control, and the selenium status, the quantity of selenium and selenylation and vulcanization reaction processes are all stably controlled.
Description
Technical field
The present invention relates to technical field of thin-film solar, more particularly to a kind of compound semiconductor film and its system
Preparation Method.
Background technology
Solar energy, as a kind of emerging energy, compared with traditional Fossil fuel, has inexhaustible, cleaning
The advantage of each side such as environmental protection.Wherein, thin-film solar cells can using cheap pottery, graphite, sheet metal etc. no
With material when substrate to manufacture, the film thickness that formation can produce voltage only needs a few micrometers, current CIGS thin-film solar
The photoelectric transformation efficiency highest of battery can reach 22.6%, and application is widely.
Compound semiconductor film series solaode (such as CIGS base, CZTS base, Sb2Se3Base and Sb2S3Base etc.
Thin-film solar cells) be efficiency highest in various thin-film solar cells, thin-film solar cells the most promising it
One.The critical process preparing above-mentioned thin-film solar cells is the compound semiconductor film prepared as light absorbing zone, and makes
Selenizing sulfuration process during standby compound semiconductor film, determines the crystalline state of semiconductive thin film and alloying component thin
Distribution in film, is the key technology of light absorbs conversion efficiency in impact compound semiconductor thin film solar cell.
The preparation method of traditional compound semiconductor film is typically first to form dorsum electrode layer on substrate, then in back of the body electricity
Form metallic film preformed layer on the layer of pole, carry out selenizing and sulfuration afterwards respectively.However, in high temperature selenidation process, it is right to be difficult to
Sample surfaces distribution selenium state and selenium amount carry out precise control so that film surface coexist simultaneously local selenium satiety and/or
Person's local owes the phenomenon of selenium, has a strong impact on sample homogeneity and selenizing quality.This is because selenium atom spatial distribution is easily subject to
To the impact of the random factor such as space thermal field and internal and external environment, thus affecting controllability and the repeatability of final technical process.
Selenium hydride. (H2Se) gas has the explosive characteristic of severe toxicity as gaseous state selenium source, there is higher production safety and environment in leading to produce
Pollution hidden trouble；And gas phase selenylation reaction speed is relatively low, the technical process of high temperature selenizing needs the time of a more than hour.?
Have using solid-state selenium in selenylation reaction, but the utilization rate of selenium is low, generally require to provide 1.4 times required for reaction to 10
Selenium again.Therefore, the preparation method of traditional compound semiconductor film not only be difficult to sample surfaces distribution selenium state with
And the amount of selenium carries out precise control, the process of selenizing and vulcanization reaction is also difficult to stability contorting, is unfavorable for applying.
Content of the invention
Based on this it is necessary to provide a kind of selenizing sulfidation in high temperature in can be to selenium state, the amount of selenium and selenizing
The process of vulcanization reaction all realizes the preparation method of the compound semiconductor film of stability contorting.
A kind of preparation method of compound semiconductor film, comprises the steps：
There is provided substrate, described substrate includes substrate, metallic film preformed layer and the solid-state selenium film being cascading；
By two described substrate parallel interval settings, and the selenium film in two described substrates is relatively；
And under the atmosphere containing gaseous state sulphur source, selenizing sulfuration is carried out simultaneously to described metallic film preformed layer, in institute
State and described compound semiconductor film is obtained on substrate.
In the preparation method of above-claimed cpd semiconductive thin film, parallel interval setting two substrates as confinement border,
Constitute confinement reaction compartment, when carrying out selenizing sulfuration simultaneously, can be by the reactant in high-temperature process and volatilization phase
Confine in above-mentioned confinement reaction compartment, thus avoid reactant running off impact out of control on course of reaction, simultaneously can be by
On microcosmic, selenium more rambunctious and the competitive reaction relation of sulfur are transferred in the macrospace regulation and control being easier to realize, thus to selenium shape
The process of state, the amount of selenium and selenizing vulcanization reaction all realizes stability contorting, is conducive to applying.
Wherein in an embodiment, the thickness of described solid-state selenium film is 0.2 μm～5 μm.
Wherein in an embodiment, the distance between two described substrates 1mm～10mm.
Wherein in an embodiment, under the atmosphere containing gaseous state sulphur source, described metallic film preformed layer is entered simultaneously
Row selenizing sulfuration step be：
The described substrate of two parallel interval settings is placed in annealing device, will be logical after described annealing device evacuation
Enter the atmosphere containing gaseous state sulphur source, heat two described substrates afterwards simultaneously, and make the temperature of two described substrates simultaneously with phase
Same heating curve is warming up to 500 DEG C～600 DEG C, and after insulation 1min～30min, slow cooling, to room temperature, completes selenizing sulfur
Change.
Wherein in an embodiment, described annealing device includes annealing furnace and two groups of heating lamp tube array, described in two groups
Heating lamp tube array is located at the side away from described solid-state selenium film for two described substrates respectively, and heats lamp tube array described in two groups
It is symmetric.
Wherein in an embodiment, the described atmosphere containing gaseous state sulphur source is the gaseous mixture of hydrogen sulfide gas and nitrogen
Body, in the mixed gas of described hydrogen sulfide gas and nitrogen, the molal quantity sum of described hydrogen sulfide and described nitrogen and described sulfur
The ratio changing the molal quantity of hydrogen is preferably 100:(1～20).
Wherein in an embodiment, described metallic film preformed layer be copper and indium gallium preformed layer, copper zinc-tin preformed layer or
Antimony preformed layer.
Wherein in an embodiment, in described copper and indium gallium preformed layer, the molal quantity sum of phosphide element and gallium element and copper
The ratio of the molal quantity of element is 100:(80～95), the ratio of the molal quantity sum with gallium element for the phosphide element and the molal quantity of gallium element
For 100:(25～40).
Wherein in an embodiment, when described metallic film preformed layer is copper and indium gallium preformed layer, in described substrate, indium unit
Element and the molal quantity sum of gallium element are 10 with the ratio of the molal quantity of selenium element:(16～18).
Additionally, also providing a kind of compound semiconductor film, using the preparation method of above-mentioned compound semiconductor film
It is prepared from.
Prepare in the preparation method of above-claimed cpd semiconductive thin film, two substrates of parallel interval setting are as confinement side
Boundary, constitutes confinement reaction compartment, when carrying out selenizing sulfuration simultaneously, can be by the reactant in high-temperature process and volatilization
Mutually confine in above-mentioned confinement reaction compartment, thus avoiding the impact out of control that reactant runs off on course of reaction, simultaneously permissible
The competitive reaction relation of selenium more rambunctious on microcosmic and sulfur is transferred in the macrospace regulation and control being easier to realize, thus to selenium
The process of state, the amount of selenium and selenizing vulcanization reaction all realizes stability contorting, is conducive to applying.
Brief description
Fig. 1 is the flow chart of the preparation method of the compound semiconductor film of an embodiment；
Fig. 2 is the schematic diagram of the substrate of an embodiment；
Fig. 3 is the position view carrying out the first substrate and the second substrate during original position selenizing sulfuration of an embodiment；
Fig. 4 (a) is the impact schematic diagram of selenium film thickness open-circuit voltage in the preparation method of CIGS thin-film；
Fig. 4 (b) is the impact schematic diagram to short-circuit current density for the selenium film thickness in the preparation method of CIGS thin-film；
Fig. 4 (c) is the impact schematic diagram to fill factor, curve factor for the selenium film thickness in the preparation method of CIGS thin-film；
Fig. 4 (d) is the impact schematic diagram to conversion efficiency for the selenium film thickness in the preparation method of CIGS thin-film；
Fig. 5 (a) is the impact with the ratio open-circuit voltage of the molal quantity sum of hydrogen sulfide and nitrogen for the molal quantity of hydrogen sulfide
Schematic diagram；
Fig. 5 (b) be the molal quantity sum of molal quantity and the hydrogen sulfide of hydrogen sulfide and nitrogen compare short-circuit current density
Impact schematic diagram；
Fig. 5 (c) is the impact comparing fill factor, curve factor with hydrogen sulfide and the molal quantity sum of nitrogen for the molal quantity of hydrogen sulfide
Schematic diagram；
Fig. 5 (d) is the impact comparing conversion efficiency with hydrogen sulfide and the molal quantity sum of nitrogen for the molal quantity of hydrogen sulfide
Schematic diagram.
Specific embodiment
Understandable for enabling the above objects, features and advantages of the present invention to become apparent from, below in conjunction with the accompanying drawings to the present invention
Specific embodiment be described in detail.Elaborate a lot of details in order to fully understand this in the following description
Bright.But the present invention can be much to implement different from alternate manner described here, and those skilled in the art can be not
Similar improvement is done, therefore the present invention is not limited by following public specific embodiment in the case of running counter to intension of the present invention.
As shown in figure 1, the preparation method of the compound semiconductor film of an embodiment, comprise the steps：
S110, offer substrate, substrate includes substrate, metallic film preformed layer and the solid-state selenium film being cascading.
See also Fig. 2, substrate includes substrate 210 and deposition dorsum electrode layer 220 over the substrate 210.First, provide
One substrate 210, the material of substrate 210 can be from soda-lime glass, flexible rustless steel or polyimide plastic etc..Permissible afterwards
Method using sputtering or evaporation deposits dorsum electrode layer 220 over the substrate 210.Dorsum electrode layer 220 can be the metal levels such as molybdenum.
Metallic film preformed layer 230 can be formed on dorsum electrode layer 220 using vapour deposition method or sputtering method.Metallic film
Preformed layer 230 can be copper and indium gallium preformed layer, copper zinc-tin preformed layer or antimony preformed layer.Certainly, according to different demands, metal
Thin film preformed layer 230 can also be the preformed layer of other metals or metal alloy.
, argon ion bombardment can be utilized in vacuum chamber accordingly golden using magnetron sputtering method taking copper and indium gallium preformed layer as a example
The target belonging to, and deposit to dorsum electrode layer 220, form copper, indium, the metallic film preformed layer 230 of gallium composition.Other metals or
The metallic film preformed layer 230 of person's metal alloy composition is similar to.
In one preferably embodiment, in above-mentioned copper and indium gallium preformed layer, the molal quantity sum of phosphide element and gallium element with
The ratio of the molal quantity of copper is 100:The molal quantity sum of (80～95), phosphide element and gallium element and the molal quantity of gallium element
Than for 100:(25～40).Research shows, because the appropriate copper vacancy defect that lean copper causes helps in CuInGaSe absorbed layer
In the efficient battery device of acquisition；The doping of simultaneously appropriate gallium element can improve the energy gap of absorbed layer, thus carrying
The open-circuit voltage parameter of high battery device.
Finally solid-state selenium film 240 can be formed on metallic film preformed layer 230 using the method for evaporation, obtain substrate
200, as shown in Figure 2.
In one preferably embodiment, in substrate 200, phosphide element and the molal quantity sum of gallium element and rubbing of selenium element
The ratio of your number is 10:(16～18).Meanwhile, the thickness of solid-state selenium film 240 is preferably 0.2 μm～5 μm.In a more excellent enforcement
In example, the thickness of solid-state selenium film 240 is 0.65 μm～1.0 μm.After there is first selenium in follow-up selenizing vulcanization reaction
Sulfur, selenium move back the competitive relation that sulfur rises, and the control of selenium pressure is very sensitive to the performance impact of final thin-film solar cells.Solid-state selenium
Film 240, as reacting unique selenium source, can make the selenium cannot be with the element of metallic film preformed layer 230 by the amount of control selenium
Occur to react completely, the sulfuration for a rear step provides reaction compartment.
, when the thickness of solid-state selenium film 240 is 0.85 μm taking copper-indium-galliun-selenium film solar cell as a example, CIGS thin-film
The conversion efficiency highest of solaode.When the thickness of solid-state selenium film 240 is less or greater than 0.85 μm, ABSORPTION EDGE blue shift or
Person's red shift, the conversion efficiency of copper-indium-galliun-selenium film solar cell all can decline.Therefore, in copper-indium-galliun-selenium film solar cell
The thickness of solid-state selenium film 240 is preferably 0.85 μm.
S120, two substrate parallel interval are arranged, and the selenium film in two substrates is relatively.
See also Fig. 3, for convenience of description, in present embodiment, two substrates 200 of step S110 are carried out area
Point, it is respectively designated as the first substrate 300 and the second substrate 400.Wherein, the first substrate 300 includes first being cascading
Substrate 310, the first dorsum electrode layer 320, the first metallic film preformed layer 330 and the first solid-state selenium film 340.Second substrate 400 wraps
Include the second substrate 410 being cascading, the second dorsum electrode layer 420, the second metallic film preformed layer 430 and the second solid-state selenium
Film 440.
As shown in figure 3, the first solid-state selenium film 340 is relative with the second solid-state selenium film 440.In one preferably embodiment,
The distance between first substrate 300 and the second substrate 400 1mm～10mm.Between the first substrate 300 and the second substrate 400
When distance is in the range of this, on the one hand, the reactant in high-temperature process and volatilization phase (selenium of such as gasification) can
Confine in space between the first substrate 300 and the second substrate 400, it is to avoid the shadow out of control that reactant runs off to course of reaction
Ring；On the other hand, the space of reaction is provided for follow-up sulfuration.
In a more excellent embodiment, the distance between the first substrate 300 and the second substrate 400 are 2mm～3mm.?
In the range of this, can preferably the reactant in high-temperature process and volatilization mutually be confined in the first substrate 300 and second
In space between substrate 400, avoid the loss of reactant to a greater degree, do not interfere with follow-up sulfidation simultaneously.
S130, under the atmosphere containing gaseous state sulphur source, selenizing sulfuration is carried out to metallic film preformed layer simultaneously, on substrate
Prepared compound semiconductor film.
Atmosphere containing gaseous state sulphur source is preferably the mixed gas of hydrogen sulfide gas and nitrogen.CIGS thin-film solar
Concentration of hydrogen sulfide in the open-circuit voltage (VOC) of battery device and reaction atmosphere has the increase relation of approximately linear.In hydrogen sulfide
Under conditions of concentration is 20%, the VOC of device can exceed 700mV.But the concentration improving merely hydrogen sulfide gas make into
The absorption bandses penetrating light narrow, and aggravate the layering of Ga component simultaneously, reduce photogenerated current and fill factor, curve factor.Therefore, consider,
In above-mentioned mixed gas, the molal quantity sum of hydrogen sulfide and nitrogen is preferably 100 with the ratio of the molal quantity of hydrogen sulfide gas:(1～
20).
Certainly, the above-mentioned atmosphere containing gaseous state sulphur source is not limited to the mixed gas of hydrogen sulfide gas and nitrogen, and nitrogen also may be used
Do not react with hydrogen sulfide and metal preformed layer under the high temperature conditions for other or the reaction such as itself does not decompose gas.
Under the atmosphere containing gaseous state sulphur source, the step simultaneously carrying out selenizing sulfuration to metallic film preformed layer is：
First substrate 300 and the second substrate 400 are placed in annealing device, by be passed through after annealing device evacuation containing
The atmosphere of gaseous state sulphur source, heats the first substrate 300 and the second substrate 400 afterwards simultaneously, and makes the first substrate 300 and the second substrate
400 temperature is warming up to 500 DEG C～600 DEG C with identical heating curve simultaneously, insulation 1min～30min after slow cooling extremely
Room temperature, completes selenizing sulfuration.
As shown in figure 3, the annealing device 500 of present embodiment includes annealing furnace 510, first heating lamp tube array 520 and
Second heating lamp tube array 530.First heating lamp tube array 520 is located at the first substrate 300 away from the one of the first solid-state selenium film 340
Side.Second heating lamp tube array 530 is located at the side away from the second solid-state selenium film 440 for second substrate 400, and the first heating fluorescent tube
Array 520 and the second heating lamp tube array 530 are symmetric.
First heating fluorescent tube 520 of present embodiment and the second heating fluorescent tube 530 are infrared halogen heating fluorescent tube.Will be upper
State the first heating fluorescent tube 520 and symmetrical can the design by temperature uniform light thermal field of the second heating fluorescent tube 530 makes heat
Amount uniform concentration, in the two-dimensional surface of the first solid-state selenium film 340 and the second solid-state selenium film 440, eliminates boundary temperature " cold-zone ".
It should be noted that in present embodiment, first the first substrate 300 and the second substrate 400 relative spacing are arranged, then
First substrate 300 and the second substrate 400 are placed in annealing device 500.But it is not limited, the order of the two can overturn.
I.e., it is possible to after first the first substrate 300 and the second substrate 400 being placed in annealing device 500, then by the first substrate 300 and
Two substrate 400 relative spacing is arranged.According to above-mentioned set-up mode, the first substrate 300 and the second substrate 400 can also be placed in and move back
After fiery device 500, naturally realize the relative spacing setting of the first substrate 300 and the second substrate 400.
The present inventor through long-term discovery of researching and analysing, selenizing sulfur in compound semiconductor film annealing process
The reaction mechanism changed is as follows：
Taking the preparation method of copper-indium-gallium-selenium semiconductor film in copper-indium-galliun-selenium film solar cell as a example, in annealing process
The dominant response approach of selenizing is as follows：
Cu+2Se→CuSe2or CuSe or Cu2Se；
In+Se→InSe or In2Se3or In2Se (lean selenium volatile phase)；
Ga+Se→GaSe or Ga2Se3or Ga2Se (lean selenium volatile phase), (binary selenides)；
InSe+CuSe→CuInSe2and InSe+1/2Cu2Se→CuInSe2and 1/2In2Se3+1/2Cu2Se=
CuInSe2；(ternary selenides)
GaSe+CuSe→CuGaSe2and GaSe+1/2Cu2Se→CuGaSe2and 1/2Ga2Se3+1/2Cu2Se=
CuGaSe2；(ternary selenides)
3CuInSe2+CuGaSe2→4CuIn0.75Ga0.25Se2(quaternary selenide).
The dominant response approach of the selenizing from above-mentioned annealing process can be seen that selenylation reaction comprises metal and selenium two
Unit, ternary and four elementary reactions, intermediate product is many, is related to solid-liquid/gas phase reaction, and course of reaction is complicated, and multicomponent reaction thing needs
To carry out mass exchange and energy exchange in reaction compartment, with the means of chemical reaction of complicated pluralism.
In the preparation method of the compound semiconductor film of the present invention, during solid-state selenium film surface temperature raises,
Solid-state selenium is first melted into liquid selenium and covers on the surface of solid-state selenium film, while forming selenylation reaction with metallic film preformed layer
Also block the too early generation of vulcanization reaction.When the surface temperature of solid-state selenium film continues to raise, not yet participate in the liquid selenium reacted
Gasification, the surface (confinement border) of solid-state selenium film as light absorbing heat carrier, by heat radiation and confinement gas microconvection
Mode and reaction compartment carry out heat exchange so that reaction compartment keeps the condition of high temperature, confines in polyatom cluster Se therein
Steam can be cracked into less elementide even monatomic state under high temperature action, continue to participate in selenylation reaction, greatly carry
The high reactivity of selenium, improves selenizing quality, reduces reactant consumption.The preparation of the compound semiconductor film of the present invention
In the selenylation reaction of method, the utilization rate of selenium can be up to more than 90%, such that it is able to the quantity delivered of precise control selenium.
Additionally, in selenidation process, the reactant such as selenium is limited in confinement space and is carried out instead with metallic film preformed layer
Should, it is to avoid run off, by adjusting confinement space size, heating curve and selenium film thickness, it is possible to obtain stablize controlled selenium and steam
Vapour pressure atmosphere, participates in selenylation reaction, thus realizing all realizing stable control to the process of selenium state, the amount of selenium and selenylation reaction
System, is conducive to applying.
Then taking the preparation method of copper-indium-gallium-selenium semiconductor film in copper-indium-galliun-selenium film solar cell as a example, in copper and indium
In the sulfidation of gallium preformed layer, S atom there may be following three kinds of reaction paths：
(1) S atom replaces out the Se atom on CIGS top layer；
(2) S atom and the element of the not metallic film preformed layer of reaction completely are reacted；
(3) S atom occupies top layer Se room.
(1st) plants the sulfuration that sulfuration mechanism is used for selenizing sufficient CIGSe film surface, and atom is replaced needs higher energy
Amount just can be carried out it is necessary to meet the harsh conditions such as higher annealing temperature and longer annealing time, and therefore rate of cure is slower.
(2nd) and (3) plant sulfuration mechanism realize it is critical only that and will introduce sulfuration before the thorough selenizing of metallic film preformed layer have pre-
The sulfuration space stayed, the formation now vulcanizing can be relatively low, so having rate of cure faster, is the preferably anti-of sulfuration in technique
Answer approach.
In the preparation method of the compound semiconductor film of the present invention, when metallic film preformed layer is deposited with solid-state selenium film
The thickness of easily controllable solid-state selenium film it is ensured that selenium can not be excessive, in order to avoid by the complete selenizing of copper and indium gallium in metallic film preformed layer.
In prior art, conventional method is that selenizing terminates revulcanization, and this requires that curing temperature is higher than selenizing temperature, because sulfur replaces
The formation of selenium can be higher, needs higher energy.The selenium of solid-state, and the density in reaction surface selenium is employed in the present invention
Height, therefore selenylation reaction is fast.And because metallic film preformed layer is not by complete selenizing, so vulcanization reaction is planted with (2nd) and (3)
Approach occurs, and curingprocess rate is fast.
The Se part on CIGSe surface is substituted by by S by sulfuration, thus forming surface C IGSSe phase.Compared with CIGSe,
The valence-band level of CIGSSe absorbed layer declines with the incorporation of S, thus having widened the band gap width Eg on light absorbing zone surface, permissible
Realize the band-gap tuning of light absorbing zone, improve the purpose of thin-film solar cells performance.When the internal excessive S component of thin film is mixed
Miscellaneous, thin film intrinsic absorption layer band gap width can be increased, and reduce the response wave band scope to absorbing incident light for the absorbed layer, thus dropping
Low device photogenerated current density, therefore S component must accumulate in film surface.
In the preparation method of the compound semiconductor film of the present invention, selenizing and vulcanization reaction achieve first selenium in time
The sulfuration of change-selenium coexists-course of reaction of after cure it is ensured that vulcanization reaction follows fast reaction approach, be rapid selenium of the present invention
Change the key that sulfuration process is realized.
By multiple analysis means of testing such as XRF, XRD and SEM, it is possible to obtain the component distribution of film compound, knot
The property of thin film feature such as crystalline state and structure and morphology, qualitative thin film course of reaction, obtains CIGS thin-film too by analysis
The substrate of sun energy battery course of reaction in the lehr is as follows：
In initial reaction stage, raise with temperature, the solid-state selenium film that the prefabricated layer surface of metallic film covers is from solid-state to liquid
Change, solid-state and liquid selenium film are fast with the reaction that on the one hand cladding improves selenizing to the good contact of metallic film preformed layer
Rate, in this stage, primary binary selenizing product initially forms in a large number, and selenium is gradually cured in thin film with compound state by elemental,
The cladding of another aspect selenium prevents the contact of hydrogen sulfide gas and metallic film preformed layer, and vulcanization reaction does not have started；With
The rising further of temperature, in thin film, binary selenides start react to each other generation ternary and/or quaternary selenide, selenium film simultaneously
Gasification, continues to participate in selenylation reaction with selenium vapor form " confinement " in film surface；After the selenium on surface is gasified totally, sample
Surface selenium vapour concentration reaches highest, and hydrogen sulfide gas come into contact with the prefabricated layer surface of CIG simultaneously, and sulfuration starts to occur.I.e. sulfur
Before change hydrogen begins participating in sulfuration, a certain degree of selenizing has completed；Subsequently selenizing vulcanization reaction is carried out simultaneously, selenizing
Reaction is gradually carried out to the inside of thin film, and sulfurization is in film surface；Proceed with reaction, selenium is depleted, permissible
Think that at this moment selenizing completes, only exist vulcanization reaction, because now internal selenizing has completed, expansion within to thin film for the sulphur atom
Dissipate and be restricted, sulfuration betides film surface, film surface Se/S ratio gradually increases direction to S and changes.
In sum, in the preparation method of the compound semiconductor film of the present invention, two substrates of parallel interval setting
As confinement border, constitute confinement reaction compartment, when carrying out selenizing sulfuration simultaneously, can be by the reaction in high-temperature process
Thing and volatilization are mutually confined in above-mentioned confinement reaction compartment, thus avoiding the shadow out of control that reactant runs off to course of reaction
Ring, the competitive reaction relation of selenium more rambunctious on microcosmic and sulfur can be transferred to the macrospace regulation and control being easier to realize simultaneously
On, thus all realizing stability contorting to the process of selenium state, the amount of selenium and selenizing vulcanization reaction, be conducive to applying.
Additionally, compared with similar production technology, the present invention has the advantages that more suitable industry Production requirements, including：This
Invention can process two pieces of substrates simultaneously, and production efficiency is high；Replace severe toxicity using safely and efficiently solid-state elemental selenium explosive
H2Se gas is as the unique selenium source in selenylation reaction, it is to avoid safety in production hidden danger；Selenizing and vulcanization reaction are in same chamber
Carry out in situ, at least subtract one item missing processing step, reduce process complexity；Relatively gaseous state selenium source, solid-state selenium has higher anti-
Should activity, at high temperature can directly and metallic element carries out selenylation reaction, the pyroprocess persistent period less than 10 minutes was
Selenizing vulcanization reaction can be completed, production time and energy consumption are greatly reduced.
The compound semiconductor film of one embodiment, using the preparation method preparation of above-mentioned compound semiconductor film
Form.
Prepare in the preparation method of above-claimed cpd semiconductive thin film, two substrates of parallel interval setting are as confinement side
Boundary, constitutes confinement reaction compartment, when carrying out selenizing sulfuration simultaneously, can be by the reactant in high-temperature process and volatilization
Mutually confine in above-mentioned confinement reaction compartment, thus avoiding the impact out of control that reactant runs off on course of reaction, simultaneously permissible
The competitive reaction relation of selenium more rambunctious on microcosmic and sulfur is transferred in the macrospace regulation and control being easier to realize, thus to selenium
The process of state, the amount of selenium and selenizing vulcanization reaction all realizes stability contorting, is conducive to applying.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Embodiment 1：
One layer of molybdenum is sputtered on the soda-lime glass substrate for 10cm*10cm for the length of side as dorsum electrode layer.
Using the copper gallium target of the gallium content with 25wt%, on molybdenum back electrode, sputtering sedimentation thickness is the copper of 250nm
Gallium thin film, then continues, with indium target, the indium thin film that sputtering sedimentation thickness is 550nm again, obtains copper and indium gallium preformed layer.
Then on copper and indium gallium preformed layer, evaporation thickness is the solid-state selenium film of 850nm, obtains substrate, substrate, the back of the body in substrate
Electrode layer, metallic film preformed layer and solid-state selenium film are cascading.
Two substrate parallel interval are arranged, and the selenium film in two substrates is relatively, the distance between two substrates are
2mm.
Two substrates of above-mentioned parallel interval setting are put in annealing device, will have the annealing furnace chamber of confined space
Evacuation then passes to the mixed gas of hydrogen sulfide gas and nitrogen, and (hydrogen sulfide gas are 5 with the mol ratio of nitrogen：95).
Light infrared halogen heating lamp tube array, uniformly heat at the back side of two substrates simultaneously and be rapidly heated, and
Make the temperature of two substrates rise to 550 DEG C with the speed of 110 DEG C/min simultaneously, be slowly dropped to room temperature after insulation 5min, obtain
Thickness is the Cu-In-Ga-Se-S thin film of 2000nm.
The cadmium sulfide of 50nm thickness is prepared by immersion method on the CIGS thin-film obtaining, then on cadmium sulphide membrane
Intrinsic zinc oxide is prepared in sputtering, then prepares one layer of conductive zinc oxide thereon again, prepares the grid of collection photovoltaics electric current afterwards again
Pole, prepares copper-indium-galliun-selenium film solar cell device.
Performance test is carried out to the copper-indium-galliun-selenium film solar cell device preparing by above-mentioned preparation method, knot
Fruit shows, above-mentioned copper-indium-galliun-selenium film solar cell device has an open-circuit voltage of 627mv, the short circuit current of 38.73mA,
0.700 fill factor, curve factor, obtains up to 17.05% conversion efficiency.Above-mentioned test result shows, to selenium shape in the present embodiment
The process of state, the amount of selenium and selenizing vulcanization reaction all achieves stability contorting, and therefore, the preparation method using the present embodiment obtains
The open-circuit voltage of the copper-indium-galliun-selenium film solar cell device arriving is higher, short circuit current is larger, fill factor, curve factor is larger, and obtains
Higher conversion efficiency, is conducive to applying.
The impact test of the photovoltaic effect to copper-indium-galliun-selenium film solar cell device for the selenium film thickness：
Several copper-indium-galliun-selenium film solar cell devices, wherein, above-mentioned preparation side are prepared using the method for embodiment 1
Only have the thickness of solid-state selenium film different in method, remaining process conditions all same.
Afterwards performance test is carried out to several copper-indium-galliun-selenium film solar cell devices above-mentioned, obtain as Fig. 4 (a)～
The test result of Fig. 4 (d).Test result shows, when the thickness of solid-state selenium film is 0.85 μm, CIGS thin-film solar electricity
The conversion efficiency highest in pond.When the thickness of solid-state selenium film is less or greater than 0.85 μm, ABSORPTION EDGE blue shift or red shift, copper and indium
The conversion efficiency of gallium selenium thin-film solar cells all can decline.Therefore, solid-state selenium film in copper-indium-galliun-selenium film solar cell
Thickness is preferably 0.85 μm.
The shadow of the photovoltaic effect to copper-indium-galliun-selenium film solar cell device for the concentration of hydrogen sulfide gas in reaction atmosphere
Ring test：
Several copper-indium-galliun-selenium film solar cell devices, wherein, above-mentioned preparation side are prepared using the method for embodiment 1
Only have the concentration of hydrogen sulfide gas in reaction atmosphere different in method, remaining process conditions all same.
Afterwards performance test is carried out to several copper-indium-galliun-selenium film solar cell devices above-mentioned, obtain as Fig. 5 (a)～
The test result of Fig. 5 (d).Test result shows, the open-circuit voltage (VOC) of copper-indium-galliun-selenium film solar cell device with reaction
Concentration of hydrogen sulfide in atmosphere has the increase relation of approximately linear.Under conditions of concentration of hydrogen sulfide is 20%, the VOC of device can
With more than 700mV, as shown in dotted line in Fig. 5 (a).But improve merely sulfuration concentration and the absorption bandses of incident illumination are narrowed,
Aggravate the layering of Ga (gallium) component simultaneously, reduce photogenerated current and fill factor, curve factor.Therefore, summary, in present embodiment
In the mixed gas of hydrogen sulfide gas and nitrogen, the molal quantity sum of hydrogen sulfide and nitrogen and the ratio of the molal quantity of hydrogen sulfide gas
It is preferably 100:(1～20).
Each technical characteristic of embodiment described above can arbitrarily be combined, for making description succinct, not to above-mentioned reality
The all possible combination of each technical characteristic applied in example is all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope of this specification record.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of preparation method of compound semiconductor film is it is characterised in that comprise the steps：
There is provided substrate, described substrate includes substrate, metallic film preformed layer and the solid-state selenium film being cascading；
By two described substrate parallel interval settings, and the selenium film in two described substrates is relatively；
And under the atmosphere containing gaseous state sulphur source, selenizing sulfuration is carried out simultaneously to described metallic film preformed layer, in described lining
Described compound semiconductor film is obtained on bottom.
2. the preparation method of compound semiconductor film according to claim 1 is it is characterised in that described solid-state selenium film
Thickness is 0.2 μm～5 μm.
3. compound semiconductor film according to claim 1 preparation method it is characterised in that two described substrates it
Between apart from 1mm～10mm.
4. the preparation method of compound semiconductor film according to claim 1 is it is characterised in that containing gaseous state sulphur source
Atmosphere under, the step simultaneously carrying out selenizing sulfuration to described metallic film preformed layer is：
The described substrate of two parallel interval settings is placed in annealing device, contains being passed through after described annealing device evacuation
There is the atmosphere of gaseous state sulphur source, heat two described substrates afterwards simultaneously, and make the temperature of two described substrates simultaneously with identical
Heating curve is warming up to 500 DEG C～600 DEG C, and after insulation 1min～30min, slow cooling, to room temperature, completes selenizing sulfuration.
5. the preparation method of compound semiconductor film according to claim 4 is it is characterised in that described annealing device bag
Include annealing furnace and two groups of heating lamp tube array, heating lamp tube array described in two groups is located at two described substrates respectively away from described solid
The side of state selenium film, and described in two groups, heating lamp tube array is symmetric.
6. the preparation method of compound semiconductor film according to claim 1 is it is characterised in that described contain gaseous sulfur
The atmosphere in source is the mixed gas of hydrogen sulfide gas and nitrogen, in the mixed gas of described hydrogen sulfide gas and nitrogen, described sulfur
Change hydrogen and the molal quantity sum of described nitrogen is preferably 100 with the ratio of the molal quantity of described hydrogen sulfide gas:(1～20).
7. the preparation method of compound semiconductor film according to claim 1 is it is characterised in that described metallic film is pre-
Preparative layer is copper and indium gallium preformed layer, copper zinc-tin preformed layer or antimony preformed layer.
8. the preparation method of compound semiconductor film according to claim 7 is it is characterised in that described copper and indium gallium is prefabricated
In layer, phosphide element and the molal quantity sum of gallium element are 100 with the ratio of the molal quantity of copper:(80～95), phosphide element and gallium
The molal quantity sum of element and the ratio of the molal quantity of gallium element are 100:(25～40).
9. the preparation method of compound semiconductor film according to claim 7 is it is characterised in that described metallic film is pre-
When preparative layer is copper and indium gallium preformed layer, in described substrate, the molal quantity sum of phosphide element and gallium element and the molal quantity of selenium element
Than for 10:(16～18).
10. a kind of compound semiconductor film is it is characterised in that adopt the compound half any one of claim 1～9
The preparation method of conductor thin film is prepared from.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378267A (en) * | 2018-09-27 | 2019-02-22 | 华中科技大学 | A kind of vulcanization molybdenum film and preparation method thereof |
| CN110581073A (en) * | 2019-09-16 | 2019-12-17 | 中国科学技术大学 | Method for preparing solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multi-layer film alloying |
| CN112968068A (en) * | 2021-02-25 | 2021-06-15 | 电子科技大学 | Inorganic solar cell based on multistage in-situ heat treatment and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547239A (en) * | 2003-12-05 | 2004-11-17 | 南开大学 | Method for preparing selenide or sulfide semiconductor film material of copper-indium-gallium |
| CN1719625A (en) * | 2005-06-03 | 2006-01-11 | 清华大学 | Process for preparing Cu-In-Ga-Se or Cu-In-Ga-S film solar battery obsorbing layer |
| US20110263072A1 (en) * | 2010-04-22 | 2011-10-27 | Taiwan Semiconductor Manufacturing Company, Ltd. | Forming chalcogenide semiconductor absorbers |
-
2016
- 2016-10-11 CN CN201610890513.3A patent/CN106409659B/en not_active Withdrawn - After Issue
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547239A (en) * | 2003-12-05 | 2004-11-17 | 南开大学 | Method for preparing selenide or sulfide semiconductor film material of copper-indium-gallium |
| CN1719625A (en) * | 2005-06-03 | 2006-01-11 | 清华大学 | Process for preparing Cu-In-Ga-Se or Cu-In-Ga-S film solar battery obsorbing layer |
| US20110263072A1 (en) * | 2010-04-22 | 2011-10-27 | Taiwan Semiconductor Manufacturing Company, Ltd. | Forming chalcogenide semiconductor absorbers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378267A (en) * | 2018-09-27 | 2019-02-22 | 华中科技大学 | A kind of vulcanization molybdenum film and preparation method thereof |
| CN109378267B (en) * | 2018-09-27 | 2021-03-26 | 华中科技大学 | Molybdenum sulfide film and preparation method thereof |
| CN110581073A (en) * | 2019-09-16 | 2019-12-17 | 中国科学技术大学 | Method for preparing solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multi-layer film alloying |
| CN110581073B (en) * | 2019-09-16 | 2022-06-14 | 中国科学技术大学 | Method for preparing solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multi-layer film alloying |
| CN112968068A (en) * | 2021-02-25 | 2021-06-15 | 电子科技大学 | Inorganic solar cell based on multistage in-situ heat treatment and preparation method thereof |
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