CN104600144A - High-efficiency copper indium gallium selenium thin-film photocell based on bulk heterojunction structure light absorption layer - Google Patents
High-efficiency copper indium gallium selenium thin-film photocell based on bulk heterojunction structure light absorption layer Download PDFInfo
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- CN104600144A CN104600144A CN201510039608.XA CN201510039608A CN104600144A CN 104600144 A CN104600144 A CN 104600144A CN 201510039608 A CN201510039608 A CN 201510039608A CN 104600144 A CN104600144 A CN 104600144A
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Abstract
The invention discloses a novel bulk heterojunction structure of an absorption layer used for a copper indium gallium selenium thin-film photocell. The bulk heterojunction structure of the absorption layer comprises p-type copper indium gallium selenium light absorption materials and an n-type cadmium sulfide nanorod which are prepared through a solution method. The novel bulk heterojunction structure not only can be prepared through the solution method and low in cost and suitable for mass production, but also effectively improves cleavage and output of photo-generated electron hole pairs due to a mixed-phase structure of bulk heterojunction. Compare with the traditional planar heterojunction, the conversion efficiency of the thin-film photocell based on the novel bulk heterojunction structure is improved by more than 15%.
Description
Technical field
The invention belongs to field of optoelectronic devices, relate to a kind of bulk heterojunction structure light-absorption layer that can be applicable to efficient Copper Indium Gallium Selenide thin film photocell newly.
Background technology
CIGS thin-film photocell has lightweight, and energy consumption is low, and light absorptive is advantages of higher more, therefore receives the extensive concern of people.But the conversion efficiency of current thin film class photovoltaic device compare with silicon-based devices general lower. in order to the energy conversion efficiency of film photovoltaic technology can be improved further, improve the right Dissociation probability of photo-generate electron-hole and charge carrier delivery efficiency is a kind of very important method. for Copper Indium Gallium Selenide, in traditional battery device, what adopt is the heterojunction structure of Copper Indium Gallium Selenide/cadmium sulfide planar structure, therefore the thickness of Copper Indium Gallium Selenide layer and crystallinity on the impact of device performance with regard to highly significant.Thickness on the one hand by increasing Copper Indium Gallium Selenide layer improves the absorption efficiency of light, require just very high to the crystallinity of film in this case, low degree of crystallinity both effectively cannot be dissociated photo-generate electron-hole to being diffused into PN junction interface, also have no idea to allow the electronics after dissociating and hole effectively export simultaneously; And the interface of p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide is limited by planar structure and cannot improves dissociation efficiency on the other hand.In order to solve such problem, we devise the bulk heterojunction structure of p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide nano-stick, adopt solwution method to prepare light absorbing zone.Because p-type and N-shaped material are together with mixing is carried, ratio by controlling mixing controls the size of different materials phase, make it suitable with the diffusion length of electron hole pair, both the interfacial area having increased pn knot improves dissociation efficiency, in turn give the effective way that charge carrier exports, so not only improve the light absorption of photovoltaic device but also therefore can not increase the compound of charge carrier.Such CIGS thin-film photocell based on bulk heterojunction structured light absorbed layer by the improvement at PN junction interface and the increase of charge carrier delivery efficiency, thus significantly improves energy conversion efficiency.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the CIGS thin-film photocell that the technical problem to be solved in the present invention is design and prepares based on bulk heterojunction structured light absorbed layer.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
Based on an efficient Copper Indium Gallium Selenide thin film photocell for bulk heterojunction structured light absorbed layer, it comprises: metal electrode; The light absorbing zone of bulk heterojunction structure; Resilient coating; Window layer; Transparent conductive substrate.
Preferably, described conductive metal film select in nickel, aluminium, gold, silver, copper, titanium, chromium one or more, but be not limited to this.
Preferably, described light absorbing zone thickness, between 0.1-10um, is lead selenide, the 4-6 race semiconductors such as vulcanized lead, cadmium sulfide, zinc sulphide, cadmium telluride, cadmium selenide, 2-6 group semiconductor nanorods and the Copper Indium Gallium Selenide such as zinc selenide, the mixture of the 1-3-5 race semiconductors such as copper-zinc-tin-sulfur, but be not limited to this, described bulk heterojunction comprises p-type Copper Indium Gallium Selenide material and n-type semiconductor nanometer rods prepared by solwution method, and wherein the length of nanometer rods is between 20-200 nanometer, and diameter is between 2-200 nanometer.
Preferably, resilient coating selects electron transport material, and thickness, between 20-200nm, is zinc oxide and titanium oxide, cadmium sulfide, the n-type semiconductor such as zinc sulphide, but is not limited to this.
Preferably, described Window layer is oxide semiconductor layer, and thickness is between 20-200 nanometer, and wherein oxide is zinc oxide, titanium oxide, and doping oxide, and wherein alloy comprises aluminium, magnesium, indium, gallium, cadmium etc. but be not limited to this.
Preferably, described conductive substrates is transparent conductive metal oxide film, and transparent conductive substrate is indium tin oxide films or the zinc-oxide film mixing aluminium, gallium, cadmium, and thickness is between 20-2000 nanometer.
The invention also discloses a kind of preparation method of above-mentioned bulk heterojunction structured light absorbed layer, wherein nano semiconductor material and Copper Indium Gallium Selenide precursor are prepared into mixed solution according to special ratios, and be prepared on metallic back electrode layer by solwution method, thickness is 200-2000 nanometer, then in inert gas, carry out thermal anneal process, heating-up temperature is that room temperature-600 is spent.
Preferably, described solwution method comprises spin-coating method, spraying process, poor modulus method, but is not limited to this.
Preferably, described Copper Indium Gallium Selenide precursor comprises Copper Indium Gallium Selenide nano material, Yi Jitong, indium, gallium metal and oxide thereof, sulfide, selenides, halogen compounds and various salts etc., but is not limited to this.
Preferably, described semi-conducting material comprises lead selenide, the 4-6 race semiconductors such as vulcanized lead, cadmium sulfide, zinc sulphide, cadmium telluride, cadmium selenide, 2-6 group semiconductors such as zinc selenide but be not limited to this.
Technique scheme has following beneficial effect: utilize solwution method to prepare the mixed film of p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide nano-stick, and thickness is greatly about 200-2000 ran.The advantage of this bulk heterojunction structure is to be prepared by solwution method on the one hand, therefore be easy to large-scale production and reduce product cost, after p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide nano-stick mix on the other hand, by blend proportion optimization, the domain size of bi-material is adjusted to the size of exciton diffusion length, effectively ensure that right the dissociating and exporting of photo-generate electron-hole.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of specification, coordinates accompanying drawing to be described in detail as follows below with preferred embodiment of the present invention.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention.
Fig. 2 is the comparison diagram that the embodiment of the present invention promotes CIGS thin-film photovoltaic cell efficiency, and wherein illustration is the electromicroscopic photograph of cadmium sulfide nano-stick.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
As shown in Figure 1, be the structural representation of the copper-indium-gallium-selenium photovoltaic device of application double-decker Window layer.This device comprises: metal back electrode 1; Bulk heterojunction structure Copper Indium Gallium Selenide light-absorption layer 2, this light-absorption layer comprises P type Copper Indium Gallium Selenide light absorbent and N-type cadmium sulfide nano-stick; N-type resilient coating 3; Window layer 4; With transparent conductive substrate 5.
Described metal back electrode 1 is conductive metal film, is generally aluminium, but is not limited to this, also comprise other metals, comprise gold, silver, copper, titanium, chromium, molybdenum etc.Metal electrode 1 is the light absorbing zone 2 of bulk heterojunction structure above, thickness is between 0.2-2um, for lead selenide, the 4-6 race semiconductors such as vulcanized lead, cadmium sulfide, zinc sulphide, cadmium telluride, cadmium selenide, 2-6 group semiconductor nanorods and the Copper Indium Gallium Selenide such as zinc selenide, the mixture of the 1-3-5 race semiconductors such as copper-zinc-tin-sulfur, but be not limited to this, described bulk heterojunction comprises p-type Copper Indium Gallium Selenide material and n-type semiconductor nanometer rods prepared by solwution method, and wherein the length of nanometer rods is between 20-200 nanometer, and diameter is between 2-200 nanometer.But be not limited to this.Resilient coating above light absorbing zone 2 selects electron transport material, and thickness, between 20-200nm, is zinc oxide and titanium oxide, cadmium sulfide, the n-type semiconductor such as zinc sulphide, but is not limited to this.Described solwution method makes a general reference all Coating Methods, as spin-coating method, and spraying process, poor modulus method etc.; Spin-coating method used, just can change the thickness of this functional layer by controlling spin speed, solution concentration and different spin coating number of times, the Main Function of this functional layer carries out light absorption, and the electron hole pair produced is dissociated and output is gone out.Light absorbing zone 2 is above Window layer, is generally zinc oxide, titanium oxide, and doping oxide, and wherein alloy comprises aluminium, magnesium, indium, gallium, cadmium etc. but be not limited to this.Being finally transparent conductive electrode 5, is oxidic transparent conductive film, and be generally indium tin oxide films or mix the zinc-oxide film of aluminium, gallium, cadmium, thickness is between 20-2000 nanometer.
Describe in detail for the preparation method of spin-coating method to the high-efficiency copper indium gallium photronic cell of above-mentioned application bulk heterojunction structured light absorbed layer below.
1. repeatedly cleaned in cleaning agent by soda-lime glass, and then through deionized water, acetone and aqueous isopropanol soak and ultrasonic each 15 minutes, finally dry up with nitrogen and through UV ozone process 15 minutes.
2. obtain method with vacuum moulding machine and prepare molybdenum electrode 800 ran.
3. by the Copper Indium Gallium Selenide/cadmium sulfide nano-stick with certain mixed proportion after filtration, (wherein the diameter of cadmium sulfide nano-stick is 20 nanometers, length is 200 nanometers) solution is with the rotating speed spin coating of 800 revs/min on the metallic substrate, after process annealing (150-350 degree), repeat same spin coating process again, reach required thickness.After completing whole spin coating, finally high temperature (250-550 degree) is annealed 30 minutes again, makes Copper Indium Gallium Selenide presoma reactive crystallization, forms continuous CIGS film, wherein containing cadmium sulfide nano-stick.
The technique preparing cadmium sulfide nano-stick is as follows:
0.54 gram of Cd (CH3COO) 2 〃 2H2O is dissolved in the mixed solvent of 117 ml deionized water and 87 milliliters of EDA; And then under stirring, add the Na2S 〃 9H2O of stoichiometric balance ratio, form white milk shape colloidal sol; Then under 80 degree, laser heating stirs and forms yellow liquid gradually in 10 hours.After having reacted, with deionized water and ethanol purge.
5. adopt CBD to make N-shaped cadmium sulfide layer
6. adopt magnetically controlled sputter method to make Window layer
7. and then with sputtering vacuum deposition method prepare indium tin oxide transparency electrode.
8. nickel/aluminium acquisition electrode is prepared in last thermal evaporation.
The bulk heterojunction structure of this novel p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide nano-stick, adopts solwution method to prepare light absorbing zone.Because p-type and N-shaped material mix, ratio by controlling mixing controls the size of different materials phase, make it suitable with the diffusion length of electron hole pair, both the interfacial area having increased pn knot improves dissociation efficiency, in turn give the effective way that charge carrier exports, so not only improve the light absorption of photovoltaic device but also therefore can not increase the compound of charge carrier.Such CIGS thin-film photocell based on bulk heterojunction structured light absorbed layer by the improvement at PN junction interface and the increase of charge carrier delivery efficiency, thus significantly improves energy conversion efficiency.
As shown in Figure 2, compare traditional light absorbing zone device, the energy conversion efficiency based on the copper-indium-gallium-selenium photovoltaic device of bulk heterojunction structured light absorbed layer improves 15%.Illustration wherein in Fig. 2 is the electromicroscopic photograph of cadmium sulfide nano-stick.
Detailed introduction that the novel bulk heterojunction structured light absorbed layer provided the embodiment of the present invention is above capable; for one of ordinary skill in the art; according to the thought of the embodiment of the present invention; all will change in specific embodiments and applications; in sum; this description should not be construed as limitation of the present invention, and all any changes made according to design philosophy of the present invention are all within protection scope of the present invention.
Claims (8)
1. a novel bulk heterojunction light-absorption layer structure, can be used for efficient film photocell, it is characterized in that, it comprises:
Metal back electrode;
Bulk heterojunction structured light absorbed layer, this absorbed layer comprises Copper Indium Gallium Selenide and cadmium sulfide nano side, and organizator heterojunction structure, is easy to the right separation of photo-generate electron-hole and output;
Resilient coating, this resilient coating and light absorbing zone form pn knot, make photo-generate electron-hole to dissociating;
Window layer;
Transparency conductive electrode.
2. photovoltaic devices according to claim 1, is characterized in that: described conductive metal film select in nickel, aluminium, gold, silver, copper, titanium, chromium one or more.
3. light absorbing zone according to claim 1, it is characterized in that: described light absorbing zone thickness is between 0.1-10um, for 4-6 race semiconductors such as lead selenide, vulcanized lead, cadmium sulfide, zinc sulphide, cadmium telluride, cadmium selenide, 2-6 group semiconductor nanorods and the Copper Indium Gallium Selenide such as zinc selenide, the mixture of the 1-3-5 race semiconductors such as copper-zinc-tin-sulfur, but be not limited to this.
4. bulk heterojunction structure according to claim 1, it is characterized in that: described bulk heterojunction comprises p-type Copper Indium Gallium Selenide material and n-type semiconductor nanometer rods prepared by solwution method, wherein the length of nanometer rods is between 20-200 nanometer, and diameter is between 2-200 nanometer.
5. resilient coating according to claim 1, it is characterized in that: described resilient coating layer material is lead selenide, the 4-6 race semiconductors such as vulcanized lead, cadmium sulfide, zinc sulphide, cadmium telluride, cadmium selenide, the 2-6 group semiconductors such as zinc selenide and 1-3-5 race semiconductor but be not limited to this, its thickness is 20-200 nanometer.
6. Window layer according to claim 1, it is characterized in that: described Window layer is oxide skin(coating) prepared by the nano oxide layer prepared of solwution method or vacuum sputtering, thickness is between 20-200 nanometer, and wherein oxide is zinc oxide, titanium oxide, and doping oxide, wherein alloy comprises aluminium, magnesium, indium, gallium, cadmium etc. but be not limited to this.
7. photovoltaic devices according to claim 1, is characterized in that: described transparent conductive film substrate is indium tin oxide films or the zinc-oxide film mixing aluminium, gallium, cadmium, and thickness is between 20-2000 nanometer.
8. be applied to a bulk heterojunction structure light-absorption layer for efficiency light battery, it is characterized in that utilizing solwution method to prepare the mixed film of p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide nano-stick, thickness is greatly about 200-2000 ran.The advantage of this bulk heterojunction structure is to be prepared by solwution method on the one hand, therefore be easy to large-scale production and reduce product cost, after p-type Copper Indium Gallium Selenide and N-shaped cadmium sulfide nano-stick mix on the other hand, by blend proportion optimization, the domain size of bi-material is adjusted to the size of exciton diffusion length, effectively ensure that right the dissociating and exporting of photo-generate electron-hole.
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| CN106975497A (en) * | 2017-03-18 | 2017-07-25 | 西北师范大学 | Titanium dioxide nanoplate and copper-zinc-tin-sulfur nano particle hetero-junctions preparation method and application |
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Application publication date: 20150506 |