CN100449791C - Compound semiconductor layer making method and solar battery using the semiconductor layer and its making method - Google Patents
Compound semiconductor layer making method and solar battery using the semiconductor layer and its making method Download PDFInfo
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- CN100449791C CN100449791C CNB200610026916XA CN200610026916A CN100449791C CN 100449791 C CN100449791 C CN 100449791C CN B200610026916X A CNB200610026916X A CN B200610026916XA CN 200610026916 A CN200610026916 A CN 200610026916A CN 100449791 C CN100449791 C CN 100449791C
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Abstract
The present invention discloses a manufacturing method of a CuInSe2 (CIS) compound semiconductor layer. In the method, a certain amount of high purity particles of Cu, Indium and Se are fully and evenly blended; the certain amount of high purity particles of Cu, Indium and Se are put in a quartz crucible, and the quartz crucible is put in a quartz atmosphere furnace in which Ar is inducted; the quartz atmosphere furnace is heated, and until the metallic particles are melted, the quartz atmosphere furnace is annealed; the quartz atmosphere furnace is cooled to the room temperature, and the crystal ingots of Cu, Indium and Se are prepared; the crystal ingots are put in the quartz atmosphere furnace for the second time to be melted and crystallized into ingots; the crystal ingots are peeled off and broken into pieces; the fragments and the base sheets of the crystal ingots are put into a quartz tube for liquid growth; Mo and Cu films are prepared in the magnetron sputtering method; the quartz tube is heated until the fragments of the crystal ingots are melted; the quartz tube is rotated clockwise at an angle of 90 DEG to ensure that melt water wets a substrate; the temperature of the melt water is lowered below the liquidus temperature, the melt water grows from liquid phase to form a single alpha phase CuInSe2 film and the semiconductor layer is used to make a solar battery. The prepared alpha-CIS film has the advantage of low structural defects and enhances the utilization rate of the solar battery and precious metal material, such as Cu, Indium and Selenium.
Description
Technical field
The present invention relates to a kind of manufacture method of compound semiconductor layer, and use this compound semiconductor layer solar cell and preparation method thereof.
Background technology
Solar cell is the element that directly transform light energy is become electric energy, its essential structure is that the semi-conductive pn joint of utilization forms, with rayed on solar cell, make the inner hole-duplet that produces of semiconductor, after P-N knot effect of electric field, the electronics (hole) that is accumulated in P-N knot both sides is drawn back formation electric current through electrode.The kind of solar cell can be divided into silicon, compound semiconductor according to material, reaches materials such as (having) machine semiconductor, then can be divided into bulk (Block) and film-type according to the material preparation kenel.
Copper indium diselenide CuInSe
2(CIS) compound solar cell because of its efficiency of light absorption height, outdoor stable performance, is the present research emphasis of solar cell in the world, and breadboard conversion efficiency is up to 19.2%.The copper indium diselenide compound has the standard of bearing proportioning (IB, IIIB and group vib components in proportions) ability that changes, has the flexibility that can change in the design that alloying component brings, and its performance long-term stability, capability of resistance to radiation is strong, there is not photic decline in the battery of preparation, is thought the best replacer of silicon materials and the candidate of space power system of future generation by consistent.
At present, people mainly adopt polynary coevaporation method or magnetron sputtering method film-forming process to prepare CuInSe
2Thin-film solar cells. these two kinds of physical vapor methods (PVD) all relate to containing selenium gas and comprise H
2Under the situation that Se exists, heating copper and indium and heat deposition selenium film on base material.Adopt H
2The shortcoming that Se carries out selenizing is H
2The toxicity of Se is very big, and is therefore very dangerous for the people of mass production environment.Although the physical vapor method can be prepared the CIS battery of high conversion efficiency, the stoicheiometry of element is difficult to accurately control, thereby utilization ratio of raw materials is low, and the noble metal waste is big, and the yields of battery is not high, and the realization of industrialization is difficulty relatively.
Polynary coevaporation method or magnetron sputtering method prepare CuInSe
2Another difficult problem that film faces is the chemical composition of control film, forms the single α phase (yellow copper structure) of copper indium diselenide compound.The mutually existing chemical composition range of α is about 5 moles of % under the normal temperature, promptly refers to if depart from CuInSe a little
21: 1: 2 fixed than composition, will not have the physics and the chemical property of α phase.Actual conditions are in the preparation process, to depart from ideal composition CuInSe a little
2Will cause another defective phase, i.e. the formation of β phase.The appearance of β phase has adverse influence to conversion efficiency of solar cell.There is the fault of construction of high concentration in the copper, indium and selenium film of physical vapor method preparation, as point defect, dislocation, grain boundary, crackle, other phase constituent or the like.These faults of construction are considered to cause the main cause of conversion efficiency of solar cell step-down usually.The light conversion efficiency record of the α-CIS film of physical vapor method (PVD) preparation at present is 18.8%.Though this conversion efficiency is very high, the theoretical value of α-CIS conversion efficiency can be up to more than 24%.Though annealing can improve the structure of CIS film, annealing also can change the composition (the particularly content of selenium) of film simultaneously.Usually the copper, indium and selenium film of physical vapor method preparation is owing to fault of construction, and its light conversion efficiency is lower than 18.8%.
Summary of the invention
The objective of the invention is in order to solve above-mentioned prior art problems, the α phase CuInSe that the liquid growth defective that provides is few
2(CIS) compound semiconductor layer, and use solar cell of this compound semiconductor and preparation method thereof.
Goal of the invention of the present invention can be achieved through the following technical solutions:
α phase CuInSe of the present invention
2(CIS) the compound semiconductor layer manufacture method is as follows:
Carry out abundant mixing after a certain amount of high purity copper (99.999%), indium (99.999%) and selenium (99.999%) particle removed surface oxide layer.The mol ratio of copper, indium, selenium element is with reference to the composition in 4 α in the composition triangle of Cu-In-Se ternary liquid phase figure-CIS primary crystallization zone.With the opening silica crucible that the element particle that mixes is packed into clean, this silica crucible is put into a quartzy atmosphere furnace.At first atmosphere furnace is vacuumized, feed Ar gas then to 820mbar.Silica crucible is warmed up to makes metallic particles fusing, the annealing 1 hour on 950 ℃ of temperature of metallic particles fusing back allows silica crucible be cooled to room temperature then, thereby makes the copper indium diselenide crystal ingot.Utilize mechanical agitation, the copper indium diselenide crystal ingot is stripped down from silica crucible.And the copper indium diselenide crystal ingot is put into quartzy atmosphere furnace carry out secondary fusion, crystallize into ingot, once more crystal ingot is stripped down from silica crucible, and crystal ingot broken into pieces, about 250mg crystal ingot fragment and substrate are put into another quartz ampoule (its bore is less than the quartz ampoule of atmosphere furnace) carry out liquid growth.Crystal ingot fragment and deposition substrate modes of emplacement are as shown in Figure 1.The substrate of putting is Cu (100nm)/Mo (1 μ m)/quartz plate.Molybdenum, copper film prepare with magnetron sputtering method.Atmosphere furnace is evacuated to 10
-5Torr, slowly the crystal ingot fragment evenly melts rising furnace (550 ℃-1020 ℃) in little quartz ampoule, then quartz ampoule is changeed 90 ° clockwise, described substrate is immersed in the copper indium diselenide fused solution, allow fused solution soak substrate, by slowly the fused solution temperature being reduced to the following 1-2 of liquidus temperature ℃, the liquidus temperature of the α-CIS primary crystallization point when liquidus temperature is the preparation crystal ingot in the composition triangle of selected Cu-In-Se ternary liquid phase figure, when the fused solution temperature is reduced to the following 1-2 of liquidus temperature ℃, liquid growth on substrate forms single α phase CuInSe
2Film.When desired thickness reaches, quartz ampoule is gone back to original position, and allow the sample cool to room temperature.
High efficiency CuInSe provided by the invention
2Thin-film solar cells as accompanying drawing 2, is Al metal electrode, ZnO:Al printing opacity reflector, CdS transition zone, P type (rich copper layer) α-CuInSe from top to bottom in regular turn
2Main absorbed layer, N type (rich indium layer) α-CuInSe
2Main absorbed layer, Mo metal electrode and quartz base plate.
Compound semiconductor layer provided by the present invention and high efficiency CuInSe
2The manufacture method of solar cell comprises following operation: utilize heating to prepare the copper indium diselenide crystal ingot; Crystal ingot broken into pieces put into quartz ampoule and add thermosetting uniform copper indium selenium fused solution; Cu (100nm)/Mo (1 μ m)/quartz plate is immersed in the fused solution, allow fused solution soak described substrate, carry out α-CuInSe by accurate control melt temperature
2Liquid growth; At prepared pure α phase CuInSe
2(CIS) adopt chemical bath method chemical bathdeposition (CBD) to make transition zone CdS on the compound semiconductor layer; On transition zone CdS, utilize RF magnetron sputtering Al
2O
3The ZnO target that mix (2～2.5%) prepares N type ZnO layer; Then with magnetron sputtering or electron beam evaporation by mask deposition of aluminum Al or silver-colored Ag film as top electrode.
Because the present invention is the method with the near-thermal equilibrium state, promptly liquid-phase growth method comes legal system to be equipped with α phase CuInSe
2(CIS) compound semiconductor layer.Prepared α-CIS film possesses the advantage that fault of construction is low, quality is high, and the α phase CuInSe of a kind of low defective, high light conversion efficiency is provided for association area
2Compound semiconductor layer.
Copper indium diselenide CuInSe of the present invention
2Solar cell be with the preparation α-CIS film be light absorbing zone, improve copper indium diselenide CuInSe effectively
2The light conversion efficiency of solar cell and the utilance of improving noble metal copper, indium, selenium material.
Description of drawings
Accompanying drawing 1 is the device schematic diagram that the present invention makes the compound semiconductor layer liquid growth;
Embodiment
Embodiment 1
For preparing above-mentioned α phase CuInSe
2(CIS) compound semiconductor film, preparation method of the present invention may further comprise the steps:
Carry out abundant mixing after a certain amount of high purity copper (99.999%), indium (99.999%) and selenium (99.999%) particle removed surface oxide layer.The mole percent of copper, indium, selenium element is respectively 5%, 60% and 35%.With the opening silica crucible that the element particle that mixes is packed into clean, this silica crucible is put into a quartzy atmosphere furnace.At first atmosphere furnace is vacuumized, feed Ar gas then to 820mbar.Silica crucible is warmed up to makes metallic particles fusing, the annealing 1 hour on 950 ℃ of temperature of metallic particles fusing back allows silica crucible be cooled to room temperature then, thereby makes the copper indium diselenide crystal ingot.Utilize mechanical agitation, the copper indium diselenide crystal ingot is stripped down from silica crucible.And the copper indium diselenide crystal ingot is put into quartzy atmosphere furnace carry out secondary fusion, crystallize into ingot, once more crystal ingot is stripped down from silica crucible, and crystal ingot broken into pieces, about 250mg crystal ingot fragment and substrate are put into another quartz ampoule (its bore is less than the quartz ampoule of atmosphere furnace) carry out liquid growth.Crystal ingot fragment and deposition substrate modes of emplacement are as shown in Figure 1.The substrate of putting is Cu (100nm)/Mo (1 μ m)/quartz plate.Molybdenum, copper film prepare with magnetron sputtering method.Atmosphere furnace is evacuated to 1.333 * 10
-3Pascal (Pa), slow rising furnace to 550 ℃, and remain on this temperature crystal ingot fragment in little quartz ampoule and evenly melt, then quartz ampoule is changeed 90 ° clockwise, described substrate is immersed in the copper indium diselenide fused solution, allow fused solution soak substrate, be lower than 1-2 ℃ by slowly the fused solution temperature being reduced to than its liquidus temperature, promptly 449 ℃, liquid growth on substrate forms single-phase CuInSe2 film.When thickness is 2m when reaching, quartz ampoule is gone back to original position, and allow the sample cool to room temperature.Prepared single-phase CuInSe2 film sample is taken out.
For the preparation (phase CuInSe2 (CIS) compound semiconductor layer, preparation method of the present invention may further comprise the steps:
Carry out abundant mixing after a certain amount of high purity copper (99.999%), indium (99.999%) and selenium (99.999%) particle removed surface oxide layer.The mole percent of copper, indium, selenium element is respectively 65%, 15% and 35%.With the opening silica crucible that the element particle that mixes is packed into clean, this silica crucible is put into a quartzy atmosphere furnace.At first atmosphere furnace is vacuumized, feed Ar gas then to 820mbar.Silica crucible is warmed up to makes metallic particles fusing, the annealing 1 hour on 950 ℃ of temperature of metallic particles fusing back allows silica crucible be cooled to room temperature then, thereby makes the copper indium diselenide crystal ingot.Utilize mechanical agitation, the copper indium diselenide crystal ingot is stripped down from silica crucible.And the copper indium diselenide crystal ingot is put into quartzy atmosphere furnace carry out secondary fusion, crystallize into ingot, once more crystal ingot is stripped down from silica crucible, and crystal ingot broken into pieces, about 450mg crystal ingot fragment and substrate are put into another quartz ampoule (its bore is less than the quartz ampoule of atmosphere furnace) carry out liquid growth.Crystal ingot fragment and deposition substrate modes of emplacement are as shown in Figure 1.The substrate of putting is Cu (100nm)/Mo (1 μ m)/quartz plate.Molybdenum, copper film prepare with magnetron sputtering method.Atmosphere furnace is evacuated to 1.333 * 10
-3Pa, slow rising furnace to 900 ℃, and remain on this temperature crystal ingot fragment in little quartz ampoule and evenly melt, then quartz ampoule is changeed 90 ° clockwise, described substrate is immersed in the copper indium diselenide fused solution, allow fused solution soak substrate, be lower than 1-2 ℃ by slowly the fused solution temperature being reduced to than its liquidus temperature, promptly 748 ℃, liquid growth on substrate forms single α phase CuInSe
2Film.When thickness is 200 μ m when reaching, quartz ampoule is gone back to original position, and allow the sample cool to room temperature.With prepared single α phase CuInSe
2Sample takes out.
Embodiment 3
Utilize the DC magnetron sputtering successively on quartz plate, to make the thick molybdenum of 1 μ m earlier, then plate the copper of 100nm.Utilize the method for embodiment 2 to make the thick P type of 2 μ m (rich copper layer) α-CuInSe at Cu (100nm)/Mo (1 μ m)/quartz plate
2Main absorbed layer utilizes the method for example 1 then to prepare the thick N type of 1 μ m (rich indium layer) α-CuInSe then
2Adopt the CBD legal system to make transition zone CdS again, comprise the steps: P type α-CuInSe
2(1 μ m)/N type α-CuInSe
2(1 μ m)/Cu (100nm)/Mo (1 μ m)/quartz plate 2h that under 350 ℃ and nitrogen atmosphere, anneals, through degreasing, steps such as rinsed with deionized water and sonic oscillation are cleaned, and put into sea water bath, be equipped with the CdS polycrystal film with the CBD legal system, film forming solution composition mol ratio is: CdCl
2: thiocarbamide [(NH
2)
2CS]: NH
4Cl: NH
4OH=2: 20: 20: 200; Solution temperature is 80 ℃, pH value 9, and through the 8min deposition, film forming is yellow homogeneous film, thickness is 50nm.
On transition zone CdS, utilize RF magnetron sputtering Al
2O
3(2%) the ZnO target of Can Zaing prepares N type ZnO layer, then with magnetron sputtering or electron beam evaporation by mask deposition of aluminum Al or silver-colored Ag film as top electrode.
Claims (7)
1. the manufacture method of a compound semiconductor layer comprises following operation:
A, copper, indium, selenium are mixed, transfer to be warmed up in the quartzy atmosphere furnace in the Ar gas shiled and make metallic particles fusing, annealing make the copper indium diselenide crystal ingot;
B, the copper indium diselenide crystal ingot is put into quartzy atmosphere furnace carry out secondary fusion, crystallize into ingot;
C, crystal ingot ground put into quartz ampoule, under vacuum condition, add thermosetting uniform copper indium selenium fused solution; Cu 100nm/Mo 1 μ m/ quartz plate is immersed in the fused solution, allow fused solution soak described substrate, by slowly the fused solution temperature being reduced to than low 1-2 ℃ of its liquidus temperature, liquid growth on substrate forms single α phase CuInSe
2Film.
2. according to the manufacture method of a kind of compound semiconductor layer of claim 1; it is characterized in that: the copper indium diselenide crystal ingot is to adopt purity to be 99.999% copper, indium and granules of selenium mixing to add hot preparation, and the mol ratio of copper, indium, selenium element is with reference to the component in 4 α in the composition triangle of Cu-In-Se ternary liquid phase figure-CIS primary crystallization zone.
3. according to the manufacture method of a kind of compound semiconductor layer of claim 1, it is characterized in that: the substrate of liquid growth is Cu 100nm/Mo 1 a μ m/ quartz plate.
4. high efficiency copper indium diselenide CuInSe
2Solar cell is characterized in that: by the rich indium layer of the N type α-CuInSe of preparation in Al metal electrode, ZnO:Al printing opacity reflector, CdS transition zone, the claim 1
2With the rich copper layer of P type α-CuInSe
2Main absorbed layer, Mo metal electrode, quartz base plate are formed.
5, a kind of high efficiency copper indium diselenide CuInSe according to claim 4
2The manufacture method of solar cell comprises following operation: utilize heating to prepare the copper indium diselenide crystal ingot; Crystal ingot broken into pieces put into quartz ampoule and add thermosetting uniform copper indium selenium fused solution; Cu 100nm/Mo 1 μ m/ quartz plate is immersed in the fused solution, allow fused solution soak described substrate, carry out α-CuInSe by accurate control melt temperature
2Liquid growth; At prepared pure α phase CuInSe
2Adopt immersion method CBD to make transition zone CdS on the compound semiconductor layer; On transition zone CdS, utilize the Al of RF magnetron sputtering 2% to 2.5%
2O
3The ZnO target that mixes prepares N type ZnO layer; Then with magnetron sputtering or electron beam evaporation by mask deposition of aluminum Al or silver-colored Ag film as top electrode.
6. a kind of high efficiency copper indium diselenide CuInSe according to claim 5
2The manufacture method of solar cell is characterized in that: the rich copper layer of P type α-CuInSe
2In the preparation process of main absorbed layer, the copper indium diselenide crystal ingot is to utilize high purity copper, indium and granules of selenium mixing to add hot preparation; The mole percent of copper, indium, selenium element is respectively 65%, 15% and 35%.
7. a kind of high efficiency copper indium diselenide CuInSe according to claim 5
2The manufacture method of solar cell is characterized in that: N type (rich indium layer) α-CuInSe
2In the preparation process of main absorbed layer, the copper indium diselenide crystal ingot is to utilize high purity copper, indium and granules of selenium mixing to add hot preparation; The mole percent of copper, indium, selenium element is respectively 5%, 60% and 35%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100449796C (en) * | 2007-06-25 | 2009-01-07 | 北京科技大学 | Making technology for light absorption layer of CuInSe2 semiconductor film solar cell |
| CN100466305C (en) * | 2007-11-22 | 2009-03-04 | 北京科技大学 | Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer |
| CN101667610B (en) * | 2009-09-09 | 2011-12-21 | 柳州百韧特先进材料有限公司 | Preparation method of critical material for absorbing layer of thin film solar cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828814A (en) * | 1985-03-13 | 1989-05-09 | Sri International | Process for purification of solid material |
| JPH08107227A (en) * | 1994-10-04 | 1996-04-23 | Yazaki Corp | Manufacturing equipment of thin film solar cell |
| CN1223474A (en) * | 1998-01-16 | 1999-07-21 | 中国地质大学（北京） | Colloidal sol-gel-selenylation processes for preparing CuInSe2 semiconductor film |
| US20060049390A1 (en) * | 2004-08-23 | 2006-03-09 | Klaus Ufert | Resistively switching nonvolatile memory cell based on alkali metal ion drift |
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2006
- 2006-05-26 CN CNB200610026916XA patent/CN100449791C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828814A (en) * | 1985-03-13 | 1989-05-09 | Sri International | Process for purification of solid material |
| JPH08107227A (en) * | 1994-10-04 | 1996-04-23 | Yazaki Corp | Manufacturing equipment of thin film solar cell |
| CN1223474A (en) * | 1998-01-16 | 1999-07-21 | 中国地质大学（北京） | Colloidal sol-gel-selenylation processes for preparing CuInSe2 semiconductor film |
| US20060049390A1 (en) * | 2004-08-23 | 2006-03-09 | Klaus Ufert | Resistively switching nonvolatile memory cell based on alkali metal ion drift |
Non-Patent Citations (1)
| Title |
|---|
| 特开平8-107227A 1996.04.23 |
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