CN102231398A - Copper-indium-gallium-selenium thin film battery with suede and preparation method - Google Patents
Copper-indium-gallium-selenium thin film battery with suede and preparation method Download PDFInfo
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- CN102231398A CN102231398A CN201110179746XA CN201110179746A CN102231398A CN 102231398 A CN102231398 A CN 102231398A CN 201110179746X A CN201110179746X A CN 201110179746XA CN 201110179746 A CN201110179746 A CN 201110179746A CN 102231398 A CN102231398 A CN 102231398A
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Abstract
The invention relates to a copper-indium-gallium-selenium thin film battery and a preparation method. The copper-indium-gallium-selenium thin film battery comprises a glass substrate, a metal back electrode layer, a light absorption layer, a buffer layer, a barrier layer and a window layer which are sequentially laminated, wherein the surface of each of the glass substrate, the metal back electrode layer, the light absorption layer, the buffer layer, the barrier layer and the window layer has suede with the same roughness. The surface of the glass substrate of the copper-indium-gallium-selenium thin film battery has the suede, and the grown thin film battery has an uneven surface, thereby functioning in trapping light. When sunlight is incident, the incident sunlight may form a certain angle with the surface of the battery due to the existence of the suede structure to further increase the probability of generating the photon-generated carriers in P-N junction areas and finally increase photo-generated current.
Description
[technical field]
The present invention relates to a kind of CIGS thin-film battery and preparation method thereof with matte.
[background technology]
In such as optoelectronic devices such as copper-indium-galliun-selenium film solar cells, in the active region of equipment, usually use light trapping to catch light.The light of catching in the equipment is many more, and the photoelectric current that light produces is big more, thereby the energy conversion efficiency of equipment is just high more.Therefore, when attempting to improve the conversion efficiency of optoelectronic device, light trapping is an important problem.
Traditional way is to adopt the surface of ground glass as sunken light face, yet the irregularity degree on traditional ground glass surface is unfavorable for producing suitable sunken light face structure much larger than the thickness of thin-film solar cells like this, and its light transmittance is also undesirable.
[summary of the invention]
Based on this, be necessary to provide a kind of sunken light effect CIGS thin-film battery and preparation method thereof preferably.
A kind of CIGS thin-film battery, comprise superimposed successively glass substrate, metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer, the surface of described glass substrate, metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer is the identical matte of roughness.
In a preferred embodiment, the matte of described glass substrate surface has the pit of a plurality of spheries, and the diameter of each pit is 3～5 microns.
In a preferred embodiment, the thickness of the matte of described glass substrate surface is 1～2 micron.
In a preferred embodiment, the thickness of described light absorbing zone is 1～1.5 micron.
A kind of preparation method of CIGS thin-film battery comprises the steps:
Make the formation matte on the surface of glass substrate; And
On described matte, form metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer successively, so that the surface of described metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer all forms the matte identical with the roughness of described glass substrate.
In a preferred embodiment, the matte of described glass substrate surface has the pit of a plurality of spheries, and the diameter of each pit is 3～5 microns.
In a preferred embodiment, described step at the surface of glass substrate making formation matte comprises:
Step 1, be the aluminium film of 200～500 nanometers, form sample at surperficial sputter one layer thickness of described glass substrate;
Step 2, the sample of step 1 is put in the quartz ampoule, in 2～3 minutes, the described glass substrate that is covered with the aluminium film is heated to 550～600 ℃, annealed then 30 minutes with iodine-tungsten lamp;
Step 3, the sample of step 2 is put into temperature is 110 ℃, and volumetric concentration is in 85% the phosphoric acid solution, to clean 5 minutes;
Step 4, the sample of step 3 is put into volume ratio is 1: 1 the hydrofluoric acid and the mixed liquor of nitric acid, etching 10～20 seconds; And
Step 5, the sample of step 4 is put in the deionized water ultrasonic cleaning 5～10 minutes.
In a preferred embodiment, in the step 4, in the mixed liquor of described hydrofluoric acid and nitric acid, the volumetric concentration of hydrofluoric acid and nitric acid is 3～5%.
In a preferred embodiment, in the step 2, the diameter of the hole of described glass substrate surface is 0.5～3 micron.
In a preferred embodiment, the thickness of the matte of described glass substrate surface is 1～2 micron.
In a preferred embodiment, the thickness of described light absorbing zone is 1～1.5 micron.
Said method is made matte at the glass substrate surface of CIGS thin-film battery, the hull cell surface irregularity that growth obtains, thus play sunken light action.When sunlight incident, because the existence of suede structure, its incident light can form certain angle (rather than vertical incidence) with battery surface, thereby increases the probability that photo-generated carrier produces in the P-N interface, finally improves photogenerated current.
[description of drawings]
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, feature and advantage of the present invention will be more clear.
Fig. 1 is the cross-sectional view of the CIGS thin-film battery of an embodiment;
Fig. 2 is the enlarged diagram at A place among Fig. 1.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.A lot of details have been set forth in the following description so that fully understand the present invention.
See also Fig. 1, the CIGS thin-film battery 100 of an embodiment comprises superimposed successively glass substrate 10, metal back electrode layer 20, light absorbing zone 30, resilient coating 40, barrier layer 50 and Window layer 60.The surface of glass substrate 10, metal back electrode layer 20, light absorbing zone 30, resilient coating 40, barrier layer 50 and Window layer 60 is the identical matte of roughness.
See also Fig. 2, the matte 11 on glass substrate 10 surfaces has the pit 12 of a plurality of spheries, and the diameter D of each pit is preferably 3～5 microns.The thickness L of the matte 11 on glass substrate 10 surfaces is preferably 1～2 micron.
Preferably, the thickness of light absorbing zone is 1～1.5 micron.
The preparation method of above-mentioned CIGS thin-film battery 100 comprises the steps:
Step S100, make on the surface of glass substrate 10 and to form matte 11.
Step S200, on matte 11, form metal back electrode layer 20, light absorbing zone 30, resilient coating 40, barrier layer 50 and Window layer 60 successively, so that the surface of metal back electrode layer 20, light absorbing zone 30, resilient coating 40, barrier layer 50 and Window layer 60 all forms the matte identical with the roughness of glass substrate 10.
Step S100 specifically comprises:
Step S101, be the aluminium film of 200～500 nanometers, form sample at surperficial sputter one layer thickness of glass substrate 10.Preferably, glass substrate 10 for surfacing, thickness is the soda-lime glass about 2mm.More preferred, plated film leaves sample in the vacuum ware in after finishing, and is oxidized to prevent the aluminium film from contacting with air.
Step S102, sample is put in the quartz ampoule, the glass substrate that will be covered with the aluminium film with iodine-tungsten lamp in 2～3 minutes is heated to 550～600 ℃, anneals then 30 minutes.
This temperature (550～600 ℃) approaches the softening point of aluminium, owing to do not soak into principle between aluminium and the glass, aluminium can be shrunk to coccoid particle, the random surface that is distributed in glass.Do not soak into principle: in the time of the aluminium of molten condition and solid-state glass contact, the adhesion layer of aluminium will shrink along glass surface, become discontinuous at the aluminum metal layer of glass surface.Alumina particles after the annealing is distributed in glass surface, and alumina particles covering place is being arranged, and generates silicon and alundum (Al.The glass ingredient of no aluminium covering place still is a silicon dioxide.
The mode of heating that adopts quartz ampoule to add iodine-tungsten lamp can shorten heating time, and can obtain good heats.
In heating process, following chemical reaction takes place in the place that the particle of aluminium contacts with the silicon of glass surface:
Al+SiO
2→Al
2O
3+Si。
Step S102, aluminium and silicon dioxide react at the diameter of the hole of glass surface generation, or perhaps the short grained diameter that aluminium film annealing after-contraction becomes is 0.5～3 micron.
Step S103, the sample of step S102 is put into temperature is 110 ℃, and volumetric concentration is in 85% the phosphoric acid solution, to clean 5 minutes.
This step mainly is to be used to clean remove residual aluminium film, and reaction equation is:
2H
3PO4+2Al→3H
2+2AlPO
4。
Step S104, the sample of step S103 is put into volume ratio is 1: 1 the hydrofluoric acid and the mixed liquor of nitric acid, etching 10～20 seconds.Preferably, in the mixed liquor of hydrofluoric acid and nitric acid, the volumetric concentration of hydrofluoric acid and nitric acid is 3～5%.
Following chemical reaction has taken place in this step:
1)：HNO
2+HNO
3→2NO
2+H
2O
2)：2NO
2+Si→Si
2++2NO
2 -
3)：Si
2++2OH
-→SiO
2+H
2
4)：SiO
2+6HF→H
2SiF
6+2H
2O
Product among the step S102 (silicon and alundum (Al) can be removed by this step, simultaneously because therefore the corrosion rate difference can form suede structure at glass surface.
Step S105, with the sample of step S104 in deionized water, use ultrasonic equipment, ultrasonic cleaning 5～10 minutes.
The effect of this step mainly is that the impurity (unreacted alumina particles remains in the acid of glass surface and the product of above-mentioned reaction) that will remain in glass surface removes.
Through above-mentioned steps, finally form matte 11 with a plurality of spherical pits on the surface of glass substrate 10, the diameter of each pit is 3～5 microns.The thickness of matte 11 is preferably 1～2 micron.The thickness of the etch period that the physics pattern of matte 11 can be by step S104 and the aluminium film of step S101 sputter is controlled.
Step S200 can adopt conventional method to prepare a plurality of layers of solar cell, for example can operate as follows:
Sputter molybdenum dorsum electrode layer on glass substrate → laser scribing P1 → Copper Indium Gallium Selenide (CIGS) light absorbing zone → high barrier layer of immersion method cadmium sulfide resilient coating → intrinsic zinc oxide → machinery line P2 → Al-Doped ZnO conductive window layer → silk screen printing slurry is to P2 groove → machinery line P3.
In other embodiment, can also be in the surperficial evaporation or the sputter MgF2 antireflection layer of Window layer, its refractive index 1.4, thickness 100 nanometers.
By said method, the suede structure of glass substrate can be transferred to the transparent conductive film of the superiors.Such structure can guarantee also reflectivity can be reduced to below 7% from 15% on the basis that makes surperficial antireflection layer.Guarantee incident light and surface at an angle, can increase the light path that light is propagated like this in the CIGS light absorbing zone, increase the probability that photo-generated carrier produces in P-N knot vicinity, thereby promote the probability that photo-generated carrier is collected greatly, further promote the efficient of copper indium gallium selenium solar cell.At irregular glass surface, the thin-film material that cladding thickness is the same, the film morphology that finally this pattern can be transferred to the superiors gets on.Wherein without any chemical reaction.
In addition, can be thinned to 1～1.5 micron to the CIGS light absorbing zone from traditional 2 microns in conjunction with this two sides light trapping structure, thereby reduced using and consuming of material and energy, shortened the Production Time of battery, fundamentally improved the energy return rate of Copper Indium Gallium Selenide battery.
The present invention makes matte at the glass substrate surface of CIGS thin-film battery, the hull cell surface irregularity that growth obtains, thus play sunken light action.When sunlight incident, because the existence of suede structure, its incident light can form certain angle (rather than vertical incidence) with battery surface (Window layer surface), thereby increase the probability that photo-generated carrier produces in the P-N interface, the final photogenerated current that improves, this effect especially has very big lifting (diffusion length is less than 0.5 micron) for the bad relatively CIGS crystal efficient of crystalline quality.Increased the light path that photon is propagated simultaneously in film, improved the absorptivity of battery, further increased the absorption region of spectrum long wave in the spectrum.For the photon of long wave, when (glass substrate surface) reflected back is surperficial from the back side, can increase the chance of total reflection, thereby further fall into light.
Adopt thinner that the Copper Indium Gallium Selenide light absorbing zone can be done in the hull cell of the present invention, less than 1 micron, when passing film, incident light arrives glass substrate, because the out-of-flatness between substrate and the electrode layer, its molybdenum layer can transfer the plane reflection of normal substrate to lambert and fall into light, thereby the increase light path is raised the efficiency.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. CIGS thin-film battery, comprise superimposed successively glass substrate, metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer, it is characterized in that: the surface of described glass substrate, metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer is the identical matte of roughness.
2. CIGS thin-film battery according to claim 1 is characterized in that: the matte of described glass substrate surface has the pit of a plurality of spheries, and the diameter of each pit is 3～5 microns.
3. CIGS thin-film battery according to claim 1 is characterized in that: the thickness of the matte of described glass substrate surface is 1～2 micron.
4. CIGS thin-film battery according to claim 1 is characterized in that: the thickness of described light absorbing zone is 1～1.5 micron.
5. the preparation method of a CIGS thin-film battery is characterized in that, comprises the steps:
Make the formation matte on the surface of glass substrate; And
On described matte, form metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer successively, so that the surface of described metal back electrode layer, light absorbing zone, resilient coating, barrier layer and Window layer all forms the matte identical with the roughness of described glass substrate.
6. the preparation method of CIGS thin-film battery according to claim 5 is characterized in that: described surface in glass substrate makes the step that forms matte and comprises:
Step 1, be the aluminium film of 200～500 nanometers, form sample at surperficial sputter one layer thickness of described glass substrate;
Step 2, the sample of step 1 is put in the quartz ampoule, in 2～3 minutes, the described glass substrate that is covered with the aluminium film is heated to 550～600 ℃, annealed then 30 minutes with iodine-tungsten lamp;
Step 3, the sample of step 2 is put into temperature is 110 ℃, and volumetric concentration is in 85% the phosphoric acid solution, to clean 5 minutes;
Step 4, the sample of step 3 is put into volume ratio is 1: 1 the hydrofluoric acid and the mixed liquor of nitric acid, etching 10～20 seconds; And
Step 5, the sample of step 4 is put in the deionized water ultrasonic cleaning 5～10 minutes.
7. the preparation method of CIGS thin-film battery according to claim 5 is characterized in that: in the step 4, in the mixed liquor of described hydrofluoric acid and nitric acid, the volumetric concentration of hydrofluoric acid and nitric acid is 3～5%.
8. the preparation method of CIGS thin-film battery according to claim 5 is characterized in that: in the step 2, the diameter of the hole of described glass substrate surface is 0.5～3 micron.
9. the preparation method of CIGS thin-film battery according to claim 5 is characterized in that: the thickness of the matte of described glass substrate surface is 1～2 micron.
10. the preparation method of CIGS thin-film battery according to claim 5 is characterized in that: the thickness of described light absorbing zone is 1～1.5 micron.
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| CN102403411A (en) * | 2011-12-07 | 2012-04-04 | 保定天威集团有限公司 | Metal back electrode of flexible film solar cell and preparation method thereof |
| CN103346200A (en) * | 2013-05-13 | 2013-10-09 | 福建铂阳精工设备有限公司 | Glass substrate and method for manufacturing the same, and method for manufacturing thin-film solar cell |
| CN103943716A (en) * | 2013-01-17 | 2014-07-23 | 上海交通大学 | Micro nano structure solar battery and preparation method of back light trapping structure thereof |
| CN104752557A (en) * | 2013-12-31 | 2015-07-01 | 中国电子科技集团公司第十八研究所 | Preparation method of light trapping structure type copper indium gallium diselenide thin film solar cell |
| WO2016188120A1 (en) * | 2015-05-25 | 2016-12-01 | 北京四方继保自动化股份有限公司 | Full-laser grooving and scribing method of large-area copper indium gallium selenide thin-film solar cell module |
| CN107994079A (en) * | 2017-08-11 | 2018-05-04 | 北京汉能光伏投资有限公司 | Flexible thin-film battery and preparation method thereof |
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| CN107994079A (en) * | 2017-08-11 | 2018-05-04 | 北京汉能光伏投资有限公司 | Flexible thin-film battery and preparation method thereof |
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Address after: Group 39, tianhuanggong village, WuJie Town, Tongzhou District, Nantong City, Jiangsu Province, 226000 Patentee after: Hanmoni (Jiangsu) Photoelectric Technology Co.,Ltd. Address before: Group 39, tianhuanggong village, WuJie Town, Tongzhou District, Nantong City, Jiangsu Province, 226000 Patentee before: Hanmoni (Jiangsu) Photoelectric Technology Co.,Ltd. |
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| CP02 | Change in the address of a patent holder |