CN101740665A - Method for preparing CdS film used for window layer of solar battery - Google Patents
Method for preparing CdS film used for window layer of solar battery Download PDFInfo
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- CN101740665A CN101740665A CN200910241693A CN200910241693A CN101740665A CN 101740665 A CN101740665 A CN 101740665A CN 200910241693 A CN200910241693 A CN 200910241693A CN 200910241693 A CN200910241693 A CN 200910241693A CN 101740665 A CN101740665 A CN 101740665A
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Abstract
The invention belongs to the technical field of the preparation of film solar batteries and discloses a method for preparing a CdS film used for a window layer of a solar battery. The method comprises the following steps of: 1, cleaning the surface of float glass by an ultrasonoscope and a chemical cleaning agent, and removing an oxide layer on the surface of the float glass by a hydrofluoric acid etching method; 2, putting the well cleaned float glass in deposition equipment to deposit a transparent electrode layer; 3, ultrasonically cleaning a substrate on which the transparent electrode layer is deposited by a chemical agent; and 4, putting the well cleaned substrate in growth equipment to grow the CdS film, and completing the preparation of the CdS window layer of the solar battery. The method has the advantages of improving performance of the device, using the CdS film to prepare solar batteries and other optical devices which are big in area and low in cost, reducing an impurity concentration of the CdS film and enhancing the quality of the CdS film.
Description
Technical field
The present invention relates to the thin-film solar cells preparing technical field, be specifically related to the method that a kind of preparation is used for the CdS film of window layer of solar battery, especially for CdS/CdTe and CdS/CIGS structure solar cell.
Background technology
In recent years, the severe day by day of international energy shortage and environmental pollution brings huge opportunity for various new energy technologies.The characteristic of solar cell inexhaustible and zero pollution with it is shown one's talent in all kinds of new energy technologies, and development at full speed has been arranged.At present, thin-film solar cells has become the main flow of development trend.In thin-film solar cells, the theoretical transformation rate of CdTe hull cell is up to 28%, and cost of manufacture is lower, thereby has attracted the extensive concern of industry.
At present, the solar cell actual converted efficient of industrialization production is subjected to the Window layer material--and the quality influence of-CdS film is very big.CdS is a kind of important semi-conducting material, and energy gap is about 2.42eV, is widely used as the window material of thin-film solar cells owing to it can allow the visible light transmissive of the overwhelming majority.So the quality of CdS film quality is huge to Solar cell performance and conversion efficiency influence, its crystalline state, surface topography and thickness all are the key factors that will consider.
Current, people have been developed the preparation method of number of C dS film, as: chemical bath deposition, the film that this technology is grown is solid inadequately, is easy to come off under the influence of external environment.Another method is as the near space sublimed method, but the film of this method growth is even inadequately, influences photopermeability.And when underlayer temperature was below or above certain value, the CdS film can't deposit, sunk to the bottom influence very big.At these practical problems, to be badly in need of finding a kind of film forming solid and even, fast growth, crystalline state are good, are not subjected to the method for substrate effect again.
Magnetically controlled sputter method is a kind ofly to have deposition rate height, film and the good material growth method of substrate adhesion property, and film density height, the easy control of components of being grown.When growing the CdS film, note substrate temperature, target performance, sputtering power, growth atmosphere and air pressure, and growth time with this method.After these parameters are groped, obtained optimized parameter.
The present invention will utilize magnetron sputtering apparatus to prepare the CdS film, and this film light permeability is good, and film forming is solid and crystalline state is good.
Summary of the invention
(1) technical problem that will solve
The object of the present invention is to provide a kind of preparation to be used for the method for the CdS film of window layer of solar battery, i.e. sputter CdS film on transparency electrode used under the different structure of solar cell.The preparation thin-film solar cells need be used transparency electrode, earlier the transparency electrode about execution deposition on glass one deck 500nm, growth CdS film on this transparent electrode layer again.Utilize diverse ways to have different effects at transparent battery material in CdS thin films, this is that the counterdiffusion effect is inevitable because transparent electrode layer and CdS Window layer are all extremely thin.If the very dark performance that promptly influences transparent electrode layer as conductive electrode in zone of diffusion makes the transmitance and the crystalline state variation of CdS Window layer again.Utilize magnetron sputtering, only need very low temperature just can realize the growth of material, greatly reduced the influence of temperature diffusion; And the growth rate of sputtering method is fast, has reduced growth time, and film forming is solid effective.Simplified the preparation process of entire device.
(2) technical scheme
For achieving the above object, the invention provides the method that a kind of preparation is used for the CdS film of window layer of solar battery, may further comprise the steps:
Step 1: utilize ultrasonic instrument and chemical lotion that the float glass surface clean is clean, and utilize the hf etching method to remove its surperficial oxide layer;
Step 2: the float glass that cleans up is put into depositing device, the deposit transparent electrode layer;
Step 3: will deposit the substrate chemical reagent ultrasonic cleaning of transparent electrode layer;
Step 4: the substrate that cleans up is put into growth apparatus, and growth CdS film is finished the preparation of solar cell CdS Window layer.
In the such scheme, chemical lotion comprises described in the step 1: acetone, ethanol and trichloroethylene.
In the such scheme, transparent electrode layer comprises described in the step 2: ITO and SnO
2: F.
In the such scheme, the thickness of transparent electrode layer described in the step 2 is 400 to 500nm.
In the such scheme, the equipment of the electrode of deposit transparent described in the step 2 comprises magnetron sputtering and chemical vapor depsotition equipment.
In the such scheme, the equipment of the CdS of growth described in the step 4 film is magnetron sputtering apparatus.
In the such scheme, during described employing magnetron sputtering apparatus growth CdS film, be to be source material with ceramic CdS target, Ar carries out as carrier gas.
In the such scheme, the film growth of CdS described in the step 4 temperature is 200 to 400 ℃, and thickness is 300 to 500nm.
(3) beneficial effect
The invention provides a kind of CdS thin-film material preparation method who is used for window layer of solar battery efficiently, the transparent electrode layer of deposition one deck 400-500nm on the promptly present float glass substrate, growth CdS film on this transparency electrode again.Major advantage has:
1, the transparency electrode that is deposited promptly can be served as the electrode of solar cell, does not influence the transmitance of sunlight and the device absorption problem to light again, and and the glass substrate adhesion strong, difficult drop-off.
2, there are not serious lattice mismatch and thermal mismatch problem between CdS film that is deposited and the transparency electrode, improved the performance of device.
Though the CdS film that 3, is deposited is polycrystalline state not, do not influence light absorption and light transmission performance, and strong adhesion, deposition rate is fast, can utilize this CdS film preparation large tracts of land, solar cell and other optics cheaply.
4, prepare in the CdS thin-film process with this sputtering method, growth temperature is low, greatly reduces CdS thin layer and transparent electrode layer counterdiffusion effect, makes impurity concentration reduction in the CdS film, has strengthened the quality of CdS film.And do not influence performances such as the thickness of transparent electrode layer and crystalline quality in the sputter procedure.
Description of drawings
For further specifying concrete technology contents of the present invention, describe breast in detail below in conjunction with embodiment and accompanying drawing after, wherein:
Fig. 1 is used for the method flow diagram of the CdS film of window layer of solar battery for preparation provided by the invention;
The membrane structure schematic diagram of Fig. 2 for being grown among the present invention;
Fig. 3 is the X-ray diffraction spectrum of the CdS film that deposits in the embodiment of the invention on ito transparent electrode;
Fig. 4 adopts the optical absorption spectra of ultraviolet-uisible spectrophotometer test for the CdS film that deposits in the embodiment of the invention on ito transparent electrode.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
Please refer to shown in Figure 1ly, Fig. 1 is used for the method flow diagram of the CdS film of window layer of solar battery for preparation provided by the invention, and this method may further comprise the steps:
Step 1: utilize ultrasonic instrument and chemical lotion that the float glass surface clean is clean, and utilize the acid system etching to remove its surperficial oxide layer.Wherein said chemical lotion comprises: acetone, ethanol and trichloroethylene;
Step 2: the float glass that cleans up is put into depositing device, deposition layer of transparent electrode layer; Wherein said transparent electrode layer comprises: ITO and SnO
2: F, the thickness of wherein said transparent electrode layer are 400 to 500nm, and the equipment of wherein said deposit transparent electrode comprises magnetron sputtering combination vapor deposition apparatus.
Step 3: will deposit the substrate chemical reagent ultrasonic cleaning of transparent electrode layer;
Step 4: the substrate that cleans up is put into growth apparatus, and growth CdS film is finished the preparation of solar cell CdS Window layer.The equipment of wherein said growth CdS film is magnetron sputtering apparatus, when adopting magnetron sputtering apparatus growth CdS film, be to be source material with ceramic CdS target, Ar carries out as carrier gas, described CdS film growth temperature is 200 to 400 ℃, and thickness is 300 to 500nm.
Embodiment one
The concrete steps of regrowth CdS film following (in conjunction with consulting Fig. 2) behind deposit transparent electrode ITO on the glass substrate:
After glass substrate is soaked in chemical lotion, substrate surface is cleaned up, and utilize nitric acid, sulfuric acid, hydrogen peroxide and hydrochloric acid to remove the inorganic matter and the oxide on surface with the ultrasonic waves for cleaning instrument;
Slowly put on the chip bench of magnetron sputtering apparatus and fix the ito transparent electrode layer of growth one deck 500nm handling clean glass substrate.Substrate temperature is 300 ℃ during sputter, and air pressure is 3 * 10
-3Pa;
With the substrate that deposited ITO with chemical lotion ultrasonic cleaning clean after, slowly put on the sputtering equipment chip bench, carry out the CdS growth for Thin Film after the fixing-stable.The magnetron sputtering apparatus of growth effect comprises radio-frequency power supply, reaction cavity, and rotatable chip bench, the target platform of placement source material, vacuum and refrigerating system, and a series of gas circuits etc.;
CdS growth for Thin Film source material is ceramic CdS target, and carrier gas is Ar during growing film.In the growth course, will feed Ar gas earlier 10 minutes, play the effect of cleaning cavity.In addition, when sputter, earlier substrate is blocked with baffle plate, target material surface is cleaned in pre-sputter 5 to 10 minutes.In the whole process, the plasma that is excited by radio-frequency power supply inspires target with the CdS in the CdS target under the control in magnetic field, then to deposit to substrate at a high speed.
When growth CdS film, substrate temperature is controlled at 200 ℃, and air pressure is 3 * 10
-3Pa, growth thickness are 500nm.
In this embodiment, we to deposit transparent electrode ITO on the glass substrate after the CdS film of regrowth carried out test analysis, comprise X-ray diffractometer, ultraviolet-uisible spectrophotometer and light at room temperature photoluminescence (PL) analysis of spectrum.Wherein, the X-ray diffraction spectrum of CdS film can be seen as shown in Figure 3 in the drawings, though the CdS film of being grown is a polycrystalline, main crystal orientation is still the axle along c, presents the growth of (002) preferred orientation, illustrates that this CdS thin film crystallization quality is good.The optical absorption spectra that Fig. 4 tests for ultraviolet-uisible spectrophotometer, by this figure as can be seen, the CdS film is very small to the absorption of visible light, can see through 80% above visible light wave range, and this conversion efficiency to solar cell is highly profitable.
Embodiment two
Deposit transparent electrode SnO on glass substrate
2: the concrete steps of regrowth CdS film following (in conjunction with consulting Fig. 2) behind the F:
After glass substrate is soaked in chemical lotion, substrate surface is cleaned up, and utilize nitric acid, sulfuric acid, hydrogen peroxide and hydrochloric acid to remove the inorganic matter and the oxide on surface with the ultrasonic waves for cleaning instrument;
Slowly put into CVD equipment on and fix the SnO of one deck 500nm that grows handling clean glass substrate
2: the F transparent electrode layer.
To deposit SnO
2: the substrate of F with chemical lotion ultrasonic cleaning clean after, slowly put on the sputtering equipment chip bench, carry out the CdS growth for Thin Film after the fixing-stable.The magnetron sputtering apparatus of growth effect comprises radio-frequency power supply, reaction cavity, and rotatable chip bench, the target platform of placement source material, vacuum and refrigerating system, and a series of gas circuits etc.;
CdS growth for Thin Film source material is ceramic CdS target, and carrier gas is Ar during growing film.In the growth course, will feed Ar gas earlier 10 minutes, play the effect of cleaning cavity.In addition, when sputter, earlier substrate is blocked with baffle plate, target material surface is cleaned in pre-sputter 5 to 10 minutes.In the whole process, the plasma that is excited by radio-frequency power supply inspires target with the CdS in the CdS target under the control in magnetic field, then to deposit to substrate at a high speed.
When growth CdS film, substrate temperature is controlled at 200 ℃, and air pressure is 3 * 10
-3Pa, growth thickness are 500nm.
In this embodiment, we to deposit transparent electrode ITO on the glass substrate after the CdS film of regrowth carried out test analysis, comprise X-ray diffractometer, ultraviolet-uisible spectrophotometer and light at room temperature photoluminescence (PL) analysis of spectrum.Wherein, the X-ray diffraction spectrum of CdS film can be seen as shown in Figure 3 in the drawings, though the CdS film of being grown is a polycrystalline, main crystal orientation is still the axle along c, presents the growth of (002) preferred orientation, illustrates that this CdS thin film crystallization quality is good.The optical absorption spectra that Fig. 4 tests for ultraviolet-uisible spectrophotometer, by this figure as can be seen, the CdS film is very small to the absorption of visible light, can see through 80% above visible light wave range, and this conversion efficiency to solar cell is highly profitable.
Embodiment three
The concrete steps of regrowth CdS film following (in conjunction with consulting Fig. 2) behind deposit transparent electrode ITO on the glass substrate:
After glass substrate is soaked in chemical lotion, substrate surface is cleaned up, and utilize nitric acid, sulfuric acid, hydrogen peroxide and hydrochloric acid to remove the inorganic matter and the oxide on surface with the ultrasonic waves for cleaning instrument;
Slowly put on the chip bench of magnetron sputtering apparatus and fix the ito transparent electrode layer of growth one deck 400nm handling clean glass substrate.Substrate temperature is 400 ℃ during sputter, and air pressure is 3 * 10
-3Pa;
With the substrate that deposited ITO with chemical lotion ultrasonic cleaning clean after, slowly put on the sputtering equipment chip bench, carry out the CdS growth for Thin Film after the fixing-stable.The magnetron sputtering apparatus of growth effect comprises radio-frequency power supply, reaction cavity, and rotatable chip bench, the target platform of placement source material, vacuum and refrigerating system, and a series of gas circuits etc.;
CdS growth for Thin Film source material is ceramic CdS target, and carrier gas is Ar during growing film.In the growth course, will feed Ar gas earlier 10 minutes, play the effect of cleaning cavity.In addition, when sputter, earlier substrate is blocked with baffle plate, target material surface is cleaned in pre-sputter 5 to 10 minutes.In the whole process, the plasma that is excited by radio-frequency power supply inspires target with the CdS in the CdS target under the control in magnetic field, then to deposit to substrate at a high speed.When growth CdS film, substrate temperature is controlled at 200 ℃, and air pressure is 3 * 10
-3Pa, growth thickness are 300nm.
Embodiment four
The concrete steps of regrowth CdS film following (in conjunction with consulting Fig. 2) behind deposit transparent electrode ITO on the glass substrate:
After glass substrate is soaked in chemical lotion, substrate surface is cleaned up, and utilize nitric acid, sulfuric acid, hydrogen peroxide and hydrochloric acid to remove the inorganic matter and the oxide on surface with the ultrasonic waves for cleaning instrument;
Slowly put on the chip bench of magnetron sputtering apparatus and fix the ito transparent electrode layer of growth one deck 500nm handling clean glass substrate.Substrate temperature is 200 ℃ during sputter, and air pressure is 3 * 10
-3Pa;
With the substrate that deposited ITO with chemical lotion ultrasonic cleaning clean after, slowly put on the sputtering equipment chip bench, carry out the CdS growth for Thin Film after the fixing-stable.The magnetron sputtering apparatus of growth effect comprises radio-frequency power supply, reaction cavity, and rotatable chip bench, the target platform of placement source material, vacuum and refrigerating system, and a series of gas circuits etc.;
CdS growth for Thin Film source material is ceramic CdS target, and carrier gas is Ar during growing film.In the growth course, will feed Ar gas earlier 10 minutes, play the effect of cleaning cavity.In addition, when sputter, earlier substrate is blocked with baffle plate, target material surface is cleaned in pre-sputter 5 to 10 minutes.In the whole process, the plasma that is excited by radio-frequency power supply inspires target with the CdS in the CdS target under the control in magnetic field, then to deposit to substrate at a high speed.When growth CdS film, substrate temperature is controlled at 200 ℃, and air pressure is 3 * 10
-3Pa, growth thickness are 400nm.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a method for preparing the CdS film that is used for window layer of solar battery is characterized in that, may further comprise the steps:
Step 1: utilize ultrasonic instrument and chemical lotion that the float glass surface clean is clean, and utilize the hf etching method to remove its surperficial oxide layer;
Step 2: the float glass that cleans up is put into depositing device, the deposit transparent electrode layer;
Step 3: will deposit the substrate chemical reagent ultrasonic cleaning of transparent electrode layer;
Step 4: the substrate that cleans up is put into growth apparatus, and growth CdS film is finished the preparation of solar cell CdS Window layer.
2. preparation according to claim 1 is used for the method for the CdS film of window layer of solar battery, it is characterized in that, chemical lotion comprises described in the step 1: acetone, ethanol and trichloroethylene.
3. preparation according to claim 1 is used for the method for the CdS film of window layer of solar battery, it is characterized in that transparent electrode layer comprises described in the step 2: ITO and SnO
2: F.
4. preparation according to claim 1 is used for the method for the CdS film of window layer of solar battery, it is characterized in that, the thickness of transparent electrode layer described in the step 2 is 400 to 500nm.
5. preparation according to claim 1 is used for the method for the CdS film of window layer of solar battery, it is characterized in that, the equipment of the electrode of deposit transparent described in the step 2 comprises magnetron sputtering and chemical vapor depsotition equipment.
6. preparation according to claim 1 is used for the method for the CdS film of window layer of solar battery, it is characterized in that, the equipment of the CdS of growth described in the step 4 film is magnetron sputtering apparatus.
7. preparation according to claim 6 is used for the method for the CdS film of window layer of solar battery, it is characterized in that, during described employing magnetron sputtering apparatus growth CdS film, is to be source material with ceramic CdS target, and Ar carries out as carrier gas.
8. preparation according to claim 1 is used for the method for the CdS film of window layer of solar battery, it is characterized in that, the film growth of CdS described in the step 4 temperature is 200 to 400 ℃, and thickness is 300 to 500nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022241A (en) * | 2011-09-28 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | High-performance transparent conductive glass module processing technology |
| CN113735160A (en) * | 2021-07-30 | 2021-12-03 | 华南师范大学 | CdS branch structure guided and grown by using Sn nanowire as template and catalytic growth method and application thereof |
-
2009
- 2009-12-02 CN CN200910241693A patent/CN101740665A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022241A (en) * | 2011-09-28 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | High-performance transparent conductive glass module processing technology |
| CN113735160A (en) * | 2021-07-30 | 2021-12-03 | 华南师范大学 | CdS branch structure guided and grown by using Sn nanowire as template and catalytic growth method and application thereof |
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Application publication date: 20100616 |