CN102102172B - Heterojunction thin film material with white light photovoltaic effect and preparation method thereof - Google Patents
Heterojunction thin film material with white light photovoltaic effect and preparation method thereof Download PDFInfo
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- CN102102172B CN102102172B CN2010105512120A CN201010551212A CN102102172B CN 102102172 B CN102102172 B CN 102102172B CN 2010105512120 A CN2010105512120 A CN 2010105512120A CN 201010551212 A CN201010551212 A CN 201010551212A CN 102102172 B CN102102172 B CN 102102172B
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Abstract
The invention discloses a heterojunction thin film material with white light photovoltaic effect and a preparation method thereof in the technical fields of the thin film solar cell material and the photoelectric device material. An n-Si(100) substrate is provided with an alumina layer and a cobalt/carbon particle film in turn so as to for the heterojunction thin film material with white light photovoltaic effect. The preparation method is as follows: the laser pulse deposition method is adopted to deposit the alumina layer and the cobalt/carbon particle film on the Si substrate. When the photoelectric film of the invention is irradiated by a 100mW/cm<2>(AM 1.5) of simulated sun light source at the room temperature, the open-circuit photovoltage of the element is up to 447mV, the short-circuit photocurrent is 18.75mA/cm<2>, the filling factor is more than 39% and the photoelectric conversion efficiency is up to 3.3%. The material of the invention has superior performances, low price and simple preparation method, does not uses any toxic, inflammable or explosive substance and is an excellent visible light sensor material and potential photovoltaic device.
Description
Technical field
The invention belongs to thin-film solar cells material and material for optoelectronic devices technical field, particularly a kind of heterogenous junction film material with white light photovoltaic effect and preparation method thereof.
Background technology
Energy shortage and environmental problem are more and more paid attention to, and photovoltaic generation receives much concern because the luminous energy of sun power directly being converted to electric energy.Before the research of photovoltaic power generation technology started from more than 100 year.1839 French physicist Bq (A.E.Becqurel) be surprised to find that, invade with two metals the voltaic cell that solution consists of, can produce extra voltaic electromotive force during illumination, he calls " photovoltaic effect " (photovoltaic effect) to this phenomenon.Semi-conductor P-N junction device photoelectric transformation efficiency in the sun is the highest, claims that usually this photovoltaic device is solar cell.Rusop has prepared the amorphous carbon-film that B adulterates/silicon heterogenous solar cell by the method for PLD.
The advantages such as the amorphous carbon film material is various because of its preparation method, and material cheaply is easy to get, and is nontoxic, and the band gap adjustability is large become the strong candidate of photoconductive material.Namita Dutta Gupta, C.Longeaud, P.Chaudhuri, A.Bhaduri, S.Vignoli, Journal of Non-Crystalline Solids, 2006,352:1307-1309 have reported the method for preparing the amorphous carbon film photoconductive material with plasma enhanced chemical vapor deposition method (PECVD).This film is very faint to the response of visible light, but very sensitive to the response of UV-light, is potential ultraviolet light detector.Document Hare Ram Aryal, Sudip Adhikari, Dilip ChandraGhimire, Golap Kalita, Masayoshi Umeno, Diamond﹠amp; Related Materials, 2008,17:680-683 and document Prakash R.Somani, Savita P.Somania, M.Umeno, Physica E, 2008,40:2783-2786 has reported and has used the microwave surface wave plasma chemical gaseous phase depositing process to prepare the method for carbon film material.A little carbon film materials are all with the gas phase process deposition, and in preparation process, a large amount of hydrocarbon gas and ammonias etc. of using, very high to preparation technology's environmental requirement and safety requirements.
Summary of the invention
The objective of the invention is to prepare a kind ofly has response to visible light at ambient temperature, can produce the heterogenous junction film material (Co of obvious photovoltaic effect
2-C
98/ Al
2O
3/ Si) and preparation method thereof.
Heterogenous junction film material with white light photovoltaic effect is provided with alumina layer and cobalt carbon granule film successively on n-Si (100) substrate, in described cobalt carbon granule film, the atomic ratio of cobalt and carbon is 2: 98, forms the Co with white light photovoltaic effect
2-C
98/ Al
2O
3/ Si heterogenous junction film material.
Described alumina layer thickness can be 2～10 nanometers.
Described cobalt carbon granule film thickness can be 60～120 nanometers.
Have the preparation method of the heterogenous junction film material of white light photovoltaic effect, the method comprises the steps:
Al with n-Si (100) substrate, purity＞99.99%
2O
3It is indoor that target and cobalt carbon target are put into the vacuum plating of pulsed laser deposition equipment, and the back end vacuum in coating chamber is evacuated to less than 4 * 10
-4After Pa, heated substrate is to 300～400 ℃ of depositing temperatures, the pulse laser bombardment aluminum oxide target that produces with the KrF laser apparatus again, beginning deposition of aluminium oxide film, deposition maintains in-situ annealing on depositing temperature after finishing, then bombards cobalt carbon target with the pulse laser that the KrF laser apparatus produces, at same temperature deposit cobalt carbon granule film, after deposition finished, sample naturally cooled to room temperature, obtains having the heterogenous junction film material of white light photovoltaic effect.
Described cobalt carbon target is to be preparation in 2: 98 with the cobalt powder of purity＞99.99% and carbon dust by the atomic ratio of cobalt and carbon, then mixes the cobalt carbon target that hot repressing becomes through wet ball grinding.
Preferred 10～20min of described in-situ annealing time.
Beneficial effect of the present invention is:
1, the material cost that adopts is low, and some samples at room temperature have obvious photovoltaic effect.The Co of PLD deposition
2-C
98/ Al
2O
3/ Si heterogenous junction film material, cobalt carbon film thickness are the p-type semi-conductor between 60～120 nanometers, alumina layer thickness is about 2～10 nanometers.The p-n junction interface of PLD deposition preparation is very smooth, and interface atom mutual diffusion is by thin layer Al
2O
3Be effectively suppressed.This optoelectronic film is under the simulated solar light source irradiation of room temperature, 100mW/cm2 (AM 1.5), and the open circuit photovoltage of device reaches 447mV, short-circuit photocurrent is 18.75mA/cm
2, packing factor is more than 39%, photoelectric transformation efficiency reaches 3.3%.Adopt this material to have superior performance, cheap, prepare the characteristics such as simple, and in preparation process, do not use any poisonous flammable and explosive substance, be a kind of visible light sensor material and potential photovoltaic device of tool of excellence.
2, adopt the pulsed laser deposition method to prepare film, method is simple, process stabilizing, and controllability is good, and is pollution-free, has very high preparation efficiency.
Description of drawings
Fig. 1: Co
2-C
98/ Al
2O
3The structure of/Si heterojunction structure thin-film material and photovoltaic performance test schematic diagram thereof;
Fig. 2: Co
2-C
98/ Al
2O
3The room temperature I-V characteristic of/Si heterojunction structure thin-film material (light and unglazed according to situation is arranged)
Number in the figure: 1-n-Si (100) substrate; 2-aluminum oxide (Al
2O
3) layer; 3-cobalt carbon (Co
2-C
98) membrana granulosa; The 4-metal electrode.
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
The present invention is a kind of Co with white light photovoltaic effect with the preparation of pulsed laser deposition method
2-C
98/ Al
2O
3/ Si heterogenous junction film material.Concrete preparation method is: first with Si (100) substrate of handling well, the Al of purity＞99.99%
2O
3It is indoor that monocrystalline target (commercial target) and cobalt carbon target are put into the vacuum plating of PLD equipment, with mechanical pump and molecular pump, the back end vacuum in coating chamber is evacuated to 4 * 10
-4After Pa, heated substrate to 300 ℃, use again KrF laser apparatus (Lambda Physics LPX205,248nm, 25ns FWHM) energy that produces is the pulsed bombardment aluminum oxide target of 360mJ, and starting simultaneously the motor of rotary target material and substrate, beginning deposition of aluminium oxide layer film maintains (300 ℃) annealing 10min on depositing temperature after the alumina layer thin film deposition finishes; Then bombard cobalt carbon target by laser pulse, (300 ℃) deposit cobalt carbon granule film at same temperature.After deposition finished, sample naturally cooled to room temperature.Cobalt carbon target used is to be preparation in 2: 98 with the cobalt powder of purity＞99.99% and carbon dust (carbon dust employing Graphite Powder 99) by the atomic ratio of cobalt and carbon, then mixes through wet ball grinding, and the cobalt carbon target that hot repressing becomes is therefore the cobalt carbon granule film of gained is Co
2-C
98Membrana granulosa.Other processing parameters in deposition process also comprise: target-substrate distance is 40mm, and the bundle spot size of laser beam on target is about 2 * 4mm, and laser repetition rate is controlled at 1～6Hz.In experiment, substrate for use is N-shaped Si (100), and resistivity is 0.55～0.8 Ω cm, and size is 10 * 5 * 0.5mm.Before experiment, substrate is put into acetone and alcohol heating ultrasonic cleaning 2 to 3 times successively, then carry out corrosion treatment with the HF acid solution that dilutes.
Prepared Co
2-C
98/ Al
2O
3Each tunic of/Si heterogenous junction film material sample is thick to be measured by TEM (JEM-2011); Co
2-C
98Membrana granulosa thickness is the p-type semi-conductor between 60～120 nanometers, alumina layer thickness is between 2～10 nanometers.The IV performance is measured by the Keithley2400 current voltmeter with comb electrode up and down vertical survey method; Light source is by 100mW/cm
2The simulated solar light source of (AM 1.5) provides.This patent is only with Co
2-C
98Membrana granulosa thickness 80 nanometers, aluminum oxide thickness are that the sample of 4 nanometers is example, provide the measuring result (Fig. 2) of schematic diagram (Fig. 1) and the photovoltaic performance of its room temperature photovoltaic performance test.
Maintain after the alumina layer thin film deposition finishes on depositing temperature (300 ℃) annealing 20min, all the other are identical with embodiment 1.
Except Co
2-C
98/ Al
2O
3Co in/Si heterojunction structure thin-film material
2-C
98Membrana granulosa thickness is 100 nanometers, and alumina layer thickness is outside 8 nanometers, and all the other are identical with embodiment 1.
Except Co
2-C
98/ Al
2O
3Co in/Si heterojunction structure thin-film material
2-C
98Membrana granulosa thickness is 80 nanometers, and alumina layer thickness is outside 2 nanometers, and all the other are identical with embodiment 1.
Except Co
2-C
98/ Al
2O
3Co in/Si heterojunction structure thin-film material
2-C
98Membrana granulosa thickness is 120 nanometers, and alumina layer thickness is outside 6 nanometers, and all the other are identical with embodiment 1.
Embodiment 6
Except the alumina layer depositing temperature is 330 ℃, deposition finishes (330 ℃) annealing 15min on depositing temperature afterwards, Co
2-C
98The membrana granulosa depositing temperature is outside 330 ℃, and all the other are identical with embodiment 1.
Embodiment 7
Except the alumina layer depositing temperature is 360 ℃, deposition finishes (360 ℃) annealing 10min on depositing temperature afterwards, Co
2-C
98The membrana granulosa depositing temperature is outside 360 ℃, and all the other are identical with embodiment 1.
Claims (6)
1. the heterogenous junction film material that has white light photovoltaic effect, it is characterized in that: be provided with successively alumina layer and cobalt carbon granule film on n-Si (100) substrate, in described cobalt carbon granule film, the atomic ratio of cobalt and carbon is 2: 98, forms the Co with white light photovoltaic effect
2-C
98/ Al
2O
3/ Si heterogenous junction film material.
2. the heterogenous junction film material with white light photovoltaic effect according to claim 1, it is characterized in that: described alumina layer thickness is in 2～10 nanometers.
3. the heterogenous junction film material with white light photovoltaic effect according to claim 1, it is characterized in that: described cobalt carbon granule film thickness is in 60～120 nanometers.
4. the described preparation method with heterogenous junction film material of white light photovoltaic effect of any one claim of claims 1 to 3, is characterized in that the method comprises the steps:
Al with n-Si (100) substrate, purity＞99.99%
2O
3It is indoor that target and cobalt carbon target are put into the vacuum plating of pulsed laser deposition equipment, and the back end vacuum in coating chamber is evacuated to less than 4 * 10
-4After Pa, heated substrate is to 300～400 ℃ of depositing temperatures, the pulse laser bombardment aluminum oxide target that produces with the KrF laser apparatus again, beginning deposition of aluminium oxide film, deposition maintains in-situ annealing on depositing temperature after finishing, then bombards cobalt carbon target with the pulse laser that the KrF laser apparatus produces, at same temperature deposit cobalt carbon granule film, described same temperature refers to identical with the depositing temperature of deposition of aluminium oxide film, after deposition finishes, forms Co
2-C
98/ Al
2O
3/ Si heterogenous junction film material treats that this material naturally cools to room temperature, obtains having the heterogenous junction film material of white light photovoltaic effect.
5. the preparation method with heterogenous junction film material of white light photovoltaic effect according to claim 4, it is characterized in that: described cobalt carbon target is to be preparation in 2: 98 with the cobalt powder of purity＞99.99% and carbon dust by the atomic ratio of cobalt and carbon, then mix the cobalt carbon target that hot repressing becomes through wet ball grinding.
6. the preparation method with heterogenous junction film material of white light photovoltaic effect according to claim 4, it is characterized in that: the in-situ annealing time is 10～20 minutes.
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| CN102569515B (en) * | 2012-01-05 | 2013-11-06 | 北京工业大学 | Preparation method for near-infrared quantum clipping film of nano pyramid light trapping structure |
| CN103255369B (en) * | 2013-06-07 | 2016-06-22 | 上海超导科技股份有限公司 | A kind of metal base band is applicable to simplification barrier layer of IBAD-MgO growth and preparation method thereof |
| CN113466977B (en) * | 2021-07-13 | 2023-01-31 | 宁波工程学院 | Surface plasmon narrow-band comb filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267745A (en) * | 2000-04-07 | 2000-09-27 | 上海交通大学 | Preparation of solar energy photovoltaic material-carbon film |
| CN101273238A (en) * | 2005-08-02 | 2008-09-24 | 桑斯翠普有限公司 | Nickel-alumina coated solar absorbers |
| CN101550530A (en) * | 2009-04-03 | 2009-10-07 | 清华大学 | Prepare iron doped carbon membrane material with white light photoconductive effect by pulse laser deposition method |
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| JP2000106446A (en) * | 1998-09-29 | 2000-04-11 | Toshiba Corp | Substrate for solar cell, solar cell and production thereof |
| US8017863B2 (en) * | 2005-11-02 | 2011-09-13 | The Regents Of The University Of Michigan | Polymer wrapped carbon nanotube near-infrared photoactive devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267745A (en) * | 2000-04-07 | 2000-09-27 | 上海交通大学 | Preparation of solar energy photovoltaic material-carbon film |
| CN101273238A (en) * | 2005-08-02 | 2008-09-24 | 桑斯翠普有限公司 | Nickel-alumina coated solar absorbers |
| CN101550530A (en) * | 2009-04-03 | 2009-10-07 | 清华大学 | Prepare iron doped carbon membrane material with white light photoconductive effect by pulse laser deposition method |
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| JP特开2000-106446A 2000.04.11 |
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