CN102983787B - Antenna solar cell and preparation method thereof - Google Patents
Antenna solar cell and preparation method thereof Download PDFInfo
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- CN102983787B CN102983787B CN201210483530.7A CN201210483530A CN102983787B CN 102983787 B CN102983787 B CN 102983787B CN 201210483530 A CN201210483530 A CN 201210483530A CN 102983787 B CN102983787 B CN 102983787B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses an antenna solar cell. The antenna solar cell comprises a template, through holes, a transparent conductive layer, metal antennae, metal oxide insulating layers and metal conductive substrates, the through holes are arranged along the thickness direction of the template, the transparent conductive layer is arranged on one surface of the template, the metal antennae, the metal oxide insulating layers and the metal conductive substrates are sequentially arranged from one end close to the transparent conductive layer to the other end in the through holes of the template, and the metal conductive substrates extend out of the through holes of the template to form back electrodes. By means of the antenna solar cell, resonance absorption and rectification can be performed to visible light, and direct current can be outwards output. The invention further discloses a preparation method of the antenna solar cell. The preparation method is combined with a magnetron sputtering method and an electrochemical deposition method to prepare the high efficiency antenna solar cell with low costs.
Description
Technical field
The present invention relates to solar cell field, particularly antenna solar cell and prepare the method for antenna solar cell in conjunction with magnetron sputtering method and electrochemical deposition method.
Background technology
Energy shortage and environmental pollution have become the major issue hindering human society sustainable development.Developing reproducible green energy resource is the important channel addressed this problem, and causes countries in the world to pay close attention to.Solar energy, as inexhaustible, the nexhaustible safely cleaning energy, is 21 century most important new forms of energy.There is problem that is inefficient and high cost because solar energy is converted into electric energy, solar energy does not also obtain large-scale commercialization utilization, its in the world's energy resource structure proportion less than 0.1%.In order to realize the large-scale commercial application of solar energy, its cost must be reduced and improve its electricity conversion.
At present as unique mature technology---the solar cell utilizing solar radiation energy to change electric energy into, its principle is the corpuscular property utilizing light, the photon excitation semiconductor namely with certain energy (>Eg) produces electron-hole pair, then utilize the internal electric field of P-N junction to be isolated, realize external output current.Exactly because like this, efficiency of solar cell is fundamentally subject to the restriction of semi-conducting material energy gap, namely cannot make full use of the energy of whole solar spectrum: energy can not be absorbed lower than the light of semiconductor Eg, energy lost with form of thermal energy higher than its redundance of light of Eg; Consider that the various compound that there is charge carrier and electric current take out the factors such as loss again, the theoretical limit efficiency (being referred to as the Shockley-Queisser limit, the S-Q limit) of single battery existence 33% under not optically focused condition.
Just in view of the root problem that traditional solar cell exists---inefficient, people are developing the solar cell of various efficient, new ideas, as multipotency band laminated cell, hot carrier battery, many excitons battery, frequency spectrum conversion cells etc.But the principle of all these batteries is all the corpuscular property based on light, still the S-Q limit can be limited to.
After Baily proposed this revolutionary concept of antenna solar cell in 1972 according to the fluctuation of light, arouse widespread concern and study, wherein most important two research directions are exactly: expand the resonant absorption wavelengths lower limit of reception antenna and improve the commutation frequency of rectifier.Researcher proposes the design of a lot of antenna solar cell, wherein the representational Marks of being of most is in the United States Patent (USP) (patent No. is No.330791) of 1984 propositions, and its primary structure comprises reception antenna, low pass filter, rectifier diode and DC filter.After this people prepare numerous RECTIFYING ANTENNA based on this modelling, and commutation frequency are progressively improved.Within 1988, Farber prepares broadband metal antenna, microwave (the Farber E.A. of 0.2GHz ~ 3GHz can be absorbed, " Antenna Solar Energy to ElectricityConversion.Report to the Airforce ", AF C F08635-83-C-0136,1988:Task85-6).The RECTIFYING ANTENNA of the preparation such as Yoo in 1992 reaches the transformation efficiency (Yoo of 60% and 39% respectively at 10GH and 35GHz, T.-W., Chang, K.Theoretical and experimentaldevelopment of10and35GHz rectennas.IEEE Trans.Microwave Theory Techn.1992:40 (6), 1259 – 1266).These researchs show and confirm that the detection of high-frequency signal is limited in the diode for rectification, and namely the commutation frequency limit of diode governs the frequency range that RECTIFYING ANTENNA can work.Thus the commutation frequency improving diode becomes the important directions of RECTIFYING ANTENNA development.
Because the limit commutation frequency of Schottky diode is at 5THz, much smaller than the visible frequency (375 ~ 750THz) needing rectification, therefore, sight is put into the MIM(metal-oxide-metal with high-frequency rectification characteristic by people) on tunnel diode.2002 National Institute of Standards and Technology (NIST) develop the RECTIFYING ANTENNA that can work under middle-infrared band 30THz, but its energy conversion efficiency only has 0.1% ~ 1%.Reception antenna preparation has in recent years had again certain development, Kotter etc. propose square snail conducting metal, in this, as so-called antenna electric magnetic trap (Kotter D.K., Novack S.D., Slafer W.D., Pinhero P., " Solar nantenna electromagneticcollectors ", Proc.2
ndint.conf.Energy Sustainability, 409 (2009), www.inl.gov/pdfs/nantenna.pdf).The researcher of Ai Dahua National Key Laboratory of the U.S. in 2007 prepares the planar loop antennas array that size only has 1/25 of hairline; it can carry out efficient absorption to far red light; but this technology is much to seek the method for suitable rectifier scale flush antenna array at present, therefore only absorbs and can not transform.
Though give to study widely to antenna solar cell, do not prepare practical antenna solar cell up to now abroad.Basic reason is the optical antenna being difficult to realize absorbing visible ray and the coupling embedding preparation can carrying out the MIM tunnel rectifier of rectification to high frequency.
Summary of the invention
The invention provides a kind of antenna solar cell, resonance absorption can be carried out to visible ray, rectification also externally exports direct current.
A kind of antenna solar cell, the through hole comprise template, arranging along the thickness direction of described template, be arranged on transparency conducting layer in the one side of described template and the metal antenna set gradually from the one end near described transparency conducting layer to the other end in the through hole of described template, metal oxide insulating layer and conducting metal substrate, described conducting metal substrate extends formation back electrode from the through hole of described template.
Generally, the through hole in template is multiple, and the metal antenna in each through hole forms metal antenna array.
Inventive antenna solar cell, the metal antenna of visible ray can be absorbed and MIM tunnel rectifier (metal antenna, metal oxide insulating layer and conducting metal substrate) the coupling embedding of rectification can be carried out high frequency, inventive antenna solar cell using sunlight as frequency electromagnetic waves, metal antenna is utilized to absorb this ripple, and be converted into high-frequency alternating current, then realize direct current energy output by rectification.What utilize due to it is the fluctuation feature of light, also just fundamentally overcomes conventional batteries this defect by energy gap restriction, proposes a kind of new construction optical antenna and MIM tunnel rectifier are combined as a whole.Inventive antenna solar cell achieves by the light absorption of visible light wave range and high-frequency rectification, obtains the direct current with obvious open circuit voltage and exports, achieve solar photoelectric conversion.
Described template is organic formwork or inorganic template, as preferably, described template is alumina formwork or polystyrene moulding, and these two kinds of templates all have mutually isolated regular sections passage, just can ensure that the metal antenna in each through hole can work alone.The thickness of described template is 1 μm ~ 1000 μm, to ensure that it has certain mechanical strength effective time controlling electrochemical deposition and prepare simultaneously.As preferably, the through hole in described template is multiple, and the aperture of multiple through hole is identical and be evenly distributed in described template, thus ensures the preparation of metal aerial array.The diameter of the through hole in described template is 10nm ~ 1000nm, and via densities is 1 × 10
11~ 10 × 10
11individual/cm
2, the rectification cut-off frequency of MIM tunnel rectifier is improved in the minimum through hole cross section utilizing template to provide.
Described transparency conducting layer is as electrode before inventive antenna solar cell, as preferably, described transparency conducting layer is the transparency conducting layer of zinc-oxide-base transparent conductive layer, indium oxide base transparency conducting layer, tin oxide base transparency conducting layer, cadmium oxide transparency conducting layer or deielectric-coating/medium/metal membrane structure.Above-mentioned transparency conducting layer can have good transmitance and less resistivity at visible-range.Further preferably, described zinc-oxide-base transparent conductive layer is Al-Doped ZnO (AZO) transparency conducting layer, described indium oxide base transparency conducting layer is tin-doped indium oxide (ITO) transparency conducting layer, and described tin oxide base transparency conducting layer is fluorine doped tin oxide (FTO) transparency conducting layer.Described transparency conducting layer is aluminum-doped zinc oxide transparent conductive layer, tin-doped indium oxide transparency conducting layer or fluorine doped tin oxide transparency conducting layer, above-mentioned transparency conducting layer has good light transmittance and conductivity, thus improves the electricity conversion of inventive antenna solar cell further.The thickness of described transparency conducting layer is 100nm ~ 10 μm, ensures higher light transmittance to guarantee template one side to cover completely simultaneously.
As preferably, the metal material of described metal antenna is the one in gold, silver, copper, tungsten, chromium, iron, cobalt, nickel, zinc, aluminium etc., the diameter of the metal antenna in the through hole of described template is 50nm ~ 500nm, the length of this metal antenna is 10nm ~ 200 μm, and when its length is 1/4th integral multiple absorbing optical wavelength, absorption efficiency is the highest.This metal antenna one end is connected with transparency conducting layer, and the other end is connected with metal oxide insulating layer, and it is on the one hand as accepting antenna, on the other hand, also as a part for MIM tunnel rectifier.
As preferably, described metal oxide insulating layer as the intermediate insulating layer of MIM diode, to ensure the formation of rectifier.Its thickness at below 20nm, to ensure the generation of tunneling effect, should be preferably 1 ~ 20nm simultaneously.Further preferably, described metal oxide insulating layer is nickel oxide insulators.
As preferably, the metal material of described conducting metal substrate is the one in silver, copper, nickel, zinc etc., and its effect is the layer of metal electrode forming MIM diode, can be prepared by relatively simple electrochemical process.
Present invention also offers a kind of preparation method of antenna solar cell, prepare high efficiency antenna solar cell in conjunction with magnetron sputtering method and electrochemical deposition method low cost.
A preparation method for antenna solar cell, comprises the following steps:
1) on the face of template being provided with through hole, utilize magnetron sputtering method to sputter layer of transparent conductive layer;
The through hole of template at least can seal by the thickness of transparency conducting layer;
2) using transparency conducting layer as work electrode, electrochemical deposition is adopted to divide plated metal antenna, metal oxide insulating layer and the conducting metal substrate successively of three steps, appear after full template through hole is filled in conducting metal substrate, be joined together to form back electrode, obtain antenna solar cell.
In step 1), as preferably, the condition of magnetron sputtering method is sputter 1 ~ 60 minute under sputtering power 20W ~ 200W;
Step 2) in, as preferably, in the electrolyte in adopting electrochemical deposition often to walk, the concentration of source metal is at 0.1mol/L ~ 5mol/L, and the sedimentation time often walked is 5 seconds ~ 5 hours.This sedimentary condition can be good at controlling deposition rate and ensures sedimental composition simultaneously.Different according to the thickness that will deposit, determine sedimentation time.
Source metal is selected according to the metal antenna of required deposition, metal oxide insulating layer and conducting metal substrate, in electrolyte often in step, solvent is water, source metal is the slaine of solubility, comprises one or more in the halide salt (comprising fluorine, chlorine, bromine, iodized salt) of respective metal, sulfate, phosphate, nitrate, borate etc.
Compared with prior art, tool of the present invention has the following advantages:
Inventive antenna solar cell, the metal antenna of visible ray can be absorbed and MIM tunnel rectifier (metal antenna, metal oxide insulating layer and conducting metal substrate) the coupling embedding of rectification can be carried out high frequency, using sunlight as frequency electromagnetic waves, metal antenna is utilized to absorb this ripple, and be converted into high-frequency alternating current, then realize direct current energy output by the rectification of MIM tunnel rectifier.What utilize due to it is the fluctuation feature of light, also just fundamentally overcomes conventional batteries this defect by energy gap restriction, can obtain higher photoelectric conversion efficiency.
The preparation method of inventive antenna solar cell, antenna solar cell is prepared in conjunction with magnetron sputtering method and electrochemical deposition method, preparation cost is low, the photoelectric conversion efficiency of the antenna solar cell of preparation is high, there are wide market prospects, be conducive to the marketization to promote, possess good economic benefit simultaneously.
Accompanying drawing explanation
Fig. 1 is the structural representation of inventive antenna solar cell;
Fig. 2 is the SEM surface topography map of monopole optical antenna array prepared by embodiment 1;
Fig. 3 is the SEM sectional view of monopole optical antenna array prepared by embodiment 1;
Fig. 4 is the current-voltage I-V curve of antenna solar cell under half-light prepared by embodiment 1;
Embodiment
As shown in Figure 1, antenna solar cell, the through hole comprise template 5, arranging along the thickness direction of template 5, be arranged on transparency conducting layer 1 in the one side of template 5 and the metal antenna 2 set gradually from the one end near transparency conducting layer 1 to the other end in the through hole of template 5, metal oxide insulating layer 3 and conducting metal substrate 4, conducting metal substrate 4 extends formation back electrode from the through hole of template 5.Transparency conducting layer 1 is as electrode before inventive antenna solar cell.
Embodiment 1
At anodic oxidation aluminium formwork, (template area is 1 × 1cm
2, via densities is 4 × 10
11individual/cm
2, the diameter of through hole is 210nm, and through hole is dispersed) and one side first magnetically controlled DC sputtering ito thin film, sputtering power is 150W, and sputtering time is 20 minutes, and the thickness of deposition ito thin film is 1 μm, and this ito thin film is as transparency conducting layer.
Then, be mixed with and be divided into 0.5mol/L NiSO
4, 0.5mol/L NiCl
2, 0.1mol/L H
3bO
3electrolyte, the solvent in this electrolyte is water.In template, sputtering ITO film is as work electrode, using saturated calomel electrode as reference electrode, using graphite electrode as to electrode, potentiostatic mode is adopted with this three-electrode system, work under the sedimentation potential of-0.5V and obtain Ni metal antenna in 5 minutes, metal antenna in each through hole forms metal antenna array, the diameter 200nm of metal antenna, length 3 μm, scanning electron microscopy (SEM) is adopted to observe metal antenna array, as shown in Figure 2, the mutually isolated and size regular uniform of metal antenna is shown.Scanning electron microscopy (SEM) is adopted to observe the cross section of metal antenna, as shown in Figure 3.
Then changing bath composition is 0.2mol/LNiCl
2, 0.01mol/L KCl, the solvent in this electrolyte is water, and regulates its pH value to be 8 with KOH, and the same potentiostatic mode adopting above-mentioned three-electrode system, works and obtain nickel oxide insulators in 1 minute under the sedimentation potential of-0.1V.Nickel oxide insulators thickness is 5nm.
Changing electrolyte is subsequently 0.8mol/L CuSO
4, 0.2mol/L (NH
4)
2sO
4, the solvent in this electrolyte is water, and the same potentiostatic mode adopting above-mentioned three-electrode system, works 5 hours under the sedimentation potential of-0.5V, guarantees that the second Ni metal exposes template and forms back electrode.
Before wherein changing bath deposition, template need be cleaned in deionized water for ultrasonic, to reduce contamination at every turn.
Be the current-voltage I-V curve of antenna solar cell under half-light of preparation as shown in Figure 4, show antenna solar cell, resonance absorption can be carried out to visible ray, rectification also externally exports direct current.
Embodiment 2
With 0.2M(mol/L) NiSO
4, 0.2M NiCl
2, 0.1M H
3bO
3electrolyte, under three-electrode system potentiostatic mode, the 5min that works under the sedimentation potential of-0.5V prepares Ni metal antenna array, the diameter 200nm of metal antenna, length 1 μm.All the other conditions are as embodiment 1.
Embodiment 3
With 0.5M NiSO
4, 0.5M NiCl
2, 0.1M H
3bO
3electrolyte, under three-electrode system potentiostatic mode, the 5min that works under the sedimentation potential of-1V prepares Ni metal antenna array, the diameter 200nm of metal antenna, length 4 μm.All the other conditions are as embodiment 1.
Embodiment 4
With 0.5M NiSO
4, 0.5M NiCl
2, 0.1M H
3bO
3for electrolyte, adopt three-electrode system potentiostatic mode, the 1min that works under the sedimentation potential of-0.5V prepares Ni metal antenna array, the diameter 200nm of metal antenna, length 1 μm.All the other conditions are as embodiment 1.
Embodiment 5
Take composition as 2MAgNO
3, 1M H
3bO
3electrolyte, adopt three-electrode system adopt potentiostatic mode, the 10min that works under the sedimentation potential of-1V obtains Ag metal antenna array, the diameter 200nm of metal antenna, length 10 μm.All the other conditions are as embodiment 1.
Embodiment 6
With 0.5M NiCl
2, 0.01M KCl, and regulate its pH value to be 8 with KOH, the three-electrode system that same employing is above-mentioned, obtain metal oxide (nickel oxide) insulating barrier with the 1min that works under the sedimentation potential of-0.1V, thickness is 8nm.All the other conditions are as embodiment 1.
Embodiment 7
With 0.5M NiCl
2, 0.01M KCl, and regulate its pH value to be 8 with KOH, the three-electrode system that same employing is above-mentioned, obtain metal oxide (nickel oxide) insulating barrier with the 1min that works under the sedimentation potential of-0.5V, thickness is 12nm.All the other conditions are as embodiment 1.
Embodiment 8
With 0.5M NiCl
2, 0.01M KCl, and regulate its pH value to be 8 with KOH, the three-electrode system that same employing is above-mentioned, obtain metal oxide (nickel oxide) insulating barrier with the 2min that works under the sedimentation potential of-0.1V, thickness is 18nm.All the other conditions are as embodiment 1.
Embodiment 9
With 0.8MCuSO
4, 0.2M (NH
4)
2sO
4for electrolyte, the above-mentioned three-electrode system of same employing works and within 2 hours, guarantees that the second Ni metal grows template and forms back electrode under the sedimentation potential of-1V.
Claims (7)
1. a preparation method for antenna solar cell, is characterized in that, comprises the following steps:
1) on the face of template being provided with through hole, utilize magnetron sputtering method to sputter layer of transparent conductive layer;
The through hole of template at least can seal by the thickness of transparency conducting layer;
2) using transparency conducting layer as work electrode, electrochemical deposition is adopted to divide plated metal antenna, metal oxide insulating layer and the conducting metal substrate successively of three steps, appear after full template through hole is filled in conducting metal substrate, be joined together to form back electrode, obtain antenna solar cell;
Described antenna solar cell, the through hole comprise template, arranging along the thickness direction of described template, be arranged on transparency conducting layer in the one side of described template and the metal antenna set gradually from the one end near described transparency conducting layer to the other end in the through hole of described template, metal oxide insulating layer and conducting metal substrate, described conducting metal substrate extends formation back electrode from the through hole of described template;
Described transparency conducting layer is aluminum-doped zinc oxide transparent conductive layer, tin-doped indium oxide transparency conducting layer or fluorine doped tin oxide transparency conducting layer.
2. the preparation method of antenna solar cell according to claim 1, is characterized in that, described template is alumina formwork or polystyrene moulding, and the thickness of described template is 1 μm ~ 1000 μm.
3. the preparation method of antenna solar cell according to claim 1, is characterized in that, the through hole in described template is multiple, and the aperture of multiple through hole is identical and be evenly distributed in described template.
4. the preparation method of antenna solar cell according to claim 1, is characterized in that, the thickness of described transparency conducting layer is 100nm ~ 10 μm.
5. antenna solar cell according to claim 1, the preparation method that it is characterized in that, the metal material of described metal antenna is the one in gold, silver, copper, tungsten, chromium, iron, cobalt, nickel, zinc, aluminium.
6. antenna solar cell according to claim 1, the preparation method that it is characterized in that, the diameter of the metal antenna in the through hole of described template is 50nm ~ 500nm, and the length of this metal antenna is 10nm ~ 200 μm.
7. the preparation method of antenna solar cell according to claim 1, is characterized in that, the thickness of described metal oxide insulating layer is 1nm ~ 20nm.
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| CN1855552A (en) * | 2005-03-16 | 2006-11-01 | 通用电气公司 | High efficiency inorganic nanorod-enhanced photovoltaic devices |
| CN101593760A (en) * | 2008-05-27 | 2009-12-02 | 伍彪 | A kind of novel solar battery |
| CN102067307A (en) * | 2008-06-13 | 2011-05-18 | 保罗·卡特勒 | Apparatus and system for a single element solar cell |
| CN102709399A (en) * | 2012-06-21 | 2012-10-03 | 上海理工大学 | Manufacturing method of high-efficiency nano antenna solar battery |
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| US8940117B2 (en) * | 2007-02-27 | 2015-01-27 | Microcontinuum, Inc. | Methods and systems for forming flexible multilayer structures |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1855552A (en) * | 2005-03-16 | 2006-11-01 | 通用电气公司 | High efficiency inorganic nanorod-enhanced photovoltaic devices |
| CN101593760A (en) * | 2008-05-27 | 2009-12-02 | 伍彪 | A kind of novel solar battery |
| CN102067307A (en) * | 2008-06-13 | 2011-05-18 | 保罗·卡特勒 | Apparatus and system for a single element solar cell |
| CN102709399A (en) * | 2012-06-21 | 2012-10-03 | 上海理工大学 | Manufacturing method of high-efficiency nano antenna solar battery |
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