CN102169916A - Cascade solar cell based on one-dimensional semiconductor nanomaterials and manufacture method thereof - Google Patents
Cascade solar cell based on one-dimensional semiconductor nanomaterials and manufacture method thereof Download PDFInfo
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- CN102169916A CN102169916A CN2011100388333A CN201110038833A CN102169916A CN 102169916 A CN102169916 A CN 102169916A CN 2011100388333 A CN2011100388333 A CN 2011100388333A CN 201110038833 A CN201110038833 A CN 201110038833A CN 102169916 A CN102169916 A CN 102169916A
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Abstract
The invention discloses a cascade solar cell based on one-dimensional semiconductor nanomaterials and a manufacture method thereof. The cascade solar cell is characterized in that the one-dimensional semiconductor nanomaterials are taken as light-absorption materials and conductive channels; the two ends of the cascade solar cell are asymmetric metal electrodes, wherein one end is a palladium electrode, and the other end is a scandium or yttrium electrode; the conductive channels between the asymmetric metal electrodes have n-1 virtual electrode couples, wherein the conductive channels are divided into n unit devices which are connected in series, the virtual electrode couples consist of palladium virtual electrodes and scandium or yttrium virtual electrodes which are connected together, the palladium virtual electrodes are located near one side of the scandium or yttrium electrode, and the scandium or yttrium virtual electrodes are located near one side of the palladium electrode. By introduction of the virtual electrode couples, the cascade of the cell can be realized without doping, therefore the output photovoltage of the cell is redoubled.
Description
Technical field
The present invention relates to solar cell, particularly based on the one dimension semiconductor nano material, the cascade high performance solar batteries that makes up of semiconductor carbon nanometer tube for example.
Background technology
Solar cell is an important source of earth energy as the representative of clean energy resource in the future, is various countries scientist's research focus at present.Based on the solar cell of conventional semiconductor material,,, be difficult to more large-scale application because price is higher though efficient is higher.And the one dimension semiconductor nano material has unique electrology characteristic and optical characteristics, is considered to make up the preferred material of new and effective low-cost solar battery.Carbon nano-tube has the particularly excellent properties of nearly all needs of solar cell of the efficient nano of structure opto-electronic device as the representative of one dimension semiconductor material.At first, semiconductor nano carbon pipe is the direct band gap material, has good extinction characteristic.Secondly, carbon nano-tube has high room temperature mobility, is the favorable conductive channel material.In addition, carbon nano-tube film has extremely low luminous reflectivity.The low-dimensional characteristic of carbon nano-tube also makes the photo-generated carrier multiplier effect in the carbon nano-tube be higher than corresponding bulk semiconductor material far away, and feasible solar cell photoelectric conversion efficiency based on monodimension nanometer material has the possibility that surmounts common block materials photoelectric conversion efficiency theoretical limit.The particularly important is at last, semiconductor carbon nanometer tube has perfect electron type contacting metal scandium (Sc) [Z.Y.Zhang, the X.L.Liang of being close to simultaneously, S.Wang, K.Yao, Y.F.Hu, Y.Z.Zhu, Q.Chen, W.W.Zhou, Y.Li, Y.G.Yao, J.Zhang, and L.-M.Peng, Nano Letters 7 (12) (2007) 3603] and metallic yttrium (Y) [L.Ding, S.Wang, Z.Y.Zhang, Q.S.Zeng, Z.X.Wang, T.Pei, L.J.Yang, X.L.Liang, J.Shen, Q.Chen, R.L. Cui, Y.Li, and L.-M.Peng, Nano Letters 9 (2009) 4209], and cavity type contacting metal Pd[A.Javey, J.Guo, Q.Wang, M.Lundstrom, H.J.Dai, Nature 424 (2003) 654].Adopt different metals to realize that respectively the ohmic contact in electronics and hole provides assurance for the high-performance solar cell that makes up based on carbon nano-tube.Adopt Pd and Sc contact electrode successfully to prepare high performance photodiode [S.Wang, L.H.Zhang, Z.Y.Zhang respectively at the semiconductor carbon nanometer tube two ends, L.Ding, Q.S.Zeng, Z.X.Wang, X.L.Liang, M.Gao, J.Shen, H.L.Xu, Q.Chen, R.L.Cui, Y.Li and Lian-Mao Peng, J.Phys.Chem.C 113 (2009) 6891], the photodiode of this structure has light transfer characteristic preferably.But as solar cell application, be that the output photovoltage is too little based on a significant disadvantages of the single solar cell of this structure, this mainly is because the energy gap of carbon nano-tube material is less relatively.In general, the diameter of the energy gap of semiconductor carbon nanometer tube and the nanotube relation of being inversely proportional to.The energy gap size of a semiconductor carbon nanometer tube is about E
g=0.7/d, wherein d is the diameter of carbon nano-tube.The energy gap that typical diameter is the carbon nano-tube of 2 nanometers is about 0.35 electron-volt.Consider the loss that exists in the actual light electric diode, the open circuit photovoltage that general carbon nano-tube photodiode is produced approximately has only about half of the pairing voltage of corresponding energy gap.The i.e. carbon pipe that is 2 nanometers for a typical diameter, typical photovoltage is 0.2 volt.For the application of solar cell, this magnitude of voltage is too little, has seriously hindered the practical application based on the carbon nano-tube solar cell.
For satisfying the needs of practical application, the approach that traditional solar energy module increases output open circuit voltage is that the battery with several low-voltages is together in series.The photovoltage of traditional silicon base battery is about 0.5 volt.A solar module is that about 30 batteries are together in series, and forms a solar module that can produce about 12 volts of output voltages jointly.Because the size of a solar cell is about 10 centimetres of 10 cm x, the series connection of these batteries can externally be carried out after finishing single battery very simply again.For example the anode of previous battery is linked the negative electrode of next stage battery with a lead.But for carbon nano-tube power cell, about 1.5 microns long carbon nano-tube can produce saturated open circuit photovoltage and short-circuit photocurrent, and the size of a unit light electric diode is greatly about several microns.It is unpractical by external circuit the carbon nano-tube solar cell being together in series, and also is uneconomic.The mode that the solar cell of traditional many knots cascade generally adopts tunnel junctions connects the solar cell of different materials or same material, the tunnel junctions complex process, need to consider the character coupling, multiple factor such as currents match, adopt different heavily doped materials to connect as needs, the performance of tunnel junctions has often determined the last efficient of battery.Therefore a kind of novel convenience, stable, the method that simply will be together in series based on the solar cell of one-dimensional nano structure have very important meaning for the solar energy system that makes up based on the scale of monodimension nanometer material.
Summary of the invention
The object of the present invention is to provide a kind of method that will be together in series based on the solar cell of one dimension semiconductor nano material, obtain a kind of novel tandem solar cell, improve the open circuit voltage of corresponding solar module based on the one dimension semiconductor nano material.
Technical scheme of the present invention is as follows:
A kind of tandem solar cell based on the one dimension semiconductor nano material, as light absorbent and conductive channel, its two ends are asymmetric metal electrodes with the one dimension semiconductor nano material: an end is palladium (Pd) electrode, the other end is scandium (Sc) or yttrium (Y) electrode; It is characterized in that, on the conductive channel between the described asymmetrical metal electrode, have n-1 empty electrode pair, conductive channel is divided into n the unit component that is cascaded, described empty electrode pair is made up of the empty electrode of palladium void electrode and scandium or yttrium that connects together, wherein the empty electrode of palladium is in close scandium or yttrium electrode one side, the empty electrode of scandium or yttrium is in close palladium electrode one side, and n is the positive integer greater than 1.
In the above-mentioned tandem solar cell, described one dimension semiconductor nano material can be carbon nano-tube or other one dimension semiconductor nano material, as one dimension silicon nanowires, width individual layer or double-layer graphite alkene nanometer band less than 5nm, all go for said structure, be preferably the intrinsic semiconductor carbon nano-tube.
For conductive channel is that the above-mentioned cascade of carbon nano-tube too can battery, and the conductive channel length of each unit component is preferably 1～2 micron, is spaced apart 1～2 micron between the promptly empty electrode pair, most preferably is 1.5 microns.
" empty electrode " described in the present invention be meant not and the direct-connected electrode of solar cell applied load circuit, not only served as the electrode of single battery but also played a part battery cascade to connect in tandem solar cell.Can overlap between empty electrode of palladium in the described empty electrode pair and the empty electrode of scandium (or yttrium).
Tandem solar cell of the present invention is by adding the purpose that some empty electrode pairs reach increases outside output open circuit voltage between the outer electrode (electrode that can link to each other with foreign current) of one dimension semiconductor nano material.Its principle is as follows:
Shown in Figure 1 is the semiconductive carbon nano tube photodiode of an asymmetric contact.The conductive channel of diode is about 1.5 microns intrinsic semiconductor carbon nano-tube 1 by a length and constitutes.One termination electrode 2 of carbon nano-tube 1 is made of Metal Palladium Pd, and other end electrode 3 is made of metal scandium Sc or yttrium Y.Under positive bias V effect, the current potential at Sc or Y electrode place improves, and the current potential at Pd electrode place reduces, when both differences surpass carbon nano-tube energy gap E
gDuring pairing potential difference, electronics and hole can not be injected into the conduction band (electronics) and the valence band (hole) of carbon nano-tube by corresponding Sc (or Y) electrode and Pd electrode with having potential barrier, form the electric current that increases sharply with bias voltage.Under reverse bias, the injection in electronics and hole all will cause very little reverse current, and reverse leakage current not change with reverse biased substantially through a potential barrier suitable with the carbon nano-tube energy gap.The voltage-to-current relation of this carbon nano-tube diode can be described [S.Wang with the diode equation of a standard well, Z.Y.Zhang, L.Ding, X.L. Liang, J.Shen, H.L. Xu, Q.Chen, R.L.Cui, Y.Li, and L.-M.Peng, Adv.Mater.20 (2008) 3258].As shown in Figure 2, the extraordinary match of diode equation of standard the voltage-to-current curve of unilateal conduction diode.Under light conditions, electrons excited and hole flow to Sc (or Y) electrode and Pd electrode respectively in the carbon nano-tube under the internal electric field effect of diode, produce one and compare E
g/ 2 higher slightly photovoltages (generally being about 0.2 volt).
In general, the semiconductor nano carbon pipe of one section asymmetric contact can produce the photovoltage of an about 0.1-0.2 volt under extraneous illumination.If between two outer electrodes 2 and 3, introduce the empty electrode pair 8 (as shown in Figure 3) of a Sc-Pd.This empty electrode pair 8 has been divided into an original device two sections carbon nano-tube that are cascaded.As shown in Figure 4, the conduction band of the carbon nano-tube of close Sc electrode (the right) end and the Fermi surface of this empty electrode pair 8 are evened up, the valence band of the carbon nano-tube of close Pd electrode (left side) end and the Fermi surface of this empty electrode pair are evened up, the empty electrode pair of this Sc-Pd has been divided into two unit components with an original device, the high voltage end of prime unit component has directly been linked the low-pressure end of back level unit component, formed two modules that unit component is cascaded, the open circuit voltage of module is the twice of unit component.Similarly, introduce two empty electrode pairs and will make the open circuit voltage of whole module increase to 3 times, introduce n-1 empty electrode pair and will make the open circuit voltage of module increase to n doubly.As shown in Figure 5, to in the carbon nano-tube module that comprises two unit components of a reality separately unit component measure the photovoltage obtain 0.12 volt and 0.14 volt respectively, whole module is measured total open circuit voltage of 0.24 volt, be approximately equal to two element cell photovoltage sums.In a module, the electric current of two unit components that preferably are cascaded is complementary.Also there are a little difference in the whole module photovoltage (0.24 volt) and two the unit component photovoltage sums (0.26 volt) that obtain in this experiment, difference between the two is mainly derived from the imperfect coupling of two unit components, and introduces the loss that the empty electrode pair of cascade causes inevitably.
The present invention provides the preparation method of above-mentioned tandem solar cell on the other hand, comprises the steps:
1) method by photoetching or electron beam lithography forms the pattern form of palladium electrode and the empty electrode of palladium on the one dimension semiconductor nano material, and evaporation layer of metal palladium is peeled off and removed unwanted metal level then;
2) method by photoetching or electron beam lithography forms the pattern form of scandium (or yttrium) electrode and the empty electrode of scandium (or yttrium) on the one dimension semiconductor nano material, and evaporation layer of metal scandium (or yttrium) is peeled off and removed unwanted metal level then.
Above-mentioned steps 1) and 2) in the metal layer thickness of institute evaporation be preferably 50 nanometers to 100 nanometer range.Step 1) and 2) order is adjustable, can make Metal Palladium electrode and empty electrode earlier, also can make metal scandium (or yttrium) electrode and empty electrode earlier.In empty electrode pair, empty electrode of palladium and the empty electrode of scandium (or yttrium) closely link together, can overlap between the two, the overlapping region can be that Metal Palladium is interior, metal scandium (or yttrium) outside, also can be metal scandium (or yttrium) interior, Metal Palladium is decided by the sequencing that electrode is made outside.
Above-mentioned steps 1) and 2) tandem solar cell of making will encapsulate, by the figure of photoetching or electron beam lithography formation encapsulated layer, one deck oxide of growing then wraps up device as encapsulated layer, perhaps utilizes organic encapsulating material to coat earlier.Described oxide as encapsulated layer can be logical luminescent material such as hafnium oxide, silica, and described organic encapsulating material is polymethyl methacrylate (PMMA) etc. for example.
Core of the present invention has been to propose a kind of Cascading Methods of the solar cell based on the one dimension semiconductor nano material, to improve the output photovoltage of solar cell.The technology of cascade is simple, need not to mix, and realizes the cascade of battery by introducing empty electrode pair, not only can provide effective voltage multiplication, can also greatly reduce simultaneously conventional batteries connect in by complicated technology bring expensive.
Description of drawings
Fig. 1 is a structural representation based on the carbon nano-tube diode of asymmetric contact, wherein: 1-carbon nano-tube, 2-palladium electrode, 3-scandium (or yttrium) electrode, 4-encapsulated layer, 5-substrate silica, the substrate of 6-heavily doped silicon.
Fig. 2 is the voltage-to-current curve of the carbon nano-tube diode shown in Figure 1 that obtains of experiment measuring.
Fig. 3 is a structural representation based on two units in series optical-electric modules of carbon nano-tube, wherein: 1-carbon nano-tube, 2-palladium electrode, 3-scandium (or yttrium) electrode, 7-test electrode, the empty electrode pair of 8-.
Fig. 4 be shown in Figure 3 pair of units in series optical-electric module can be with schematic diagram.
Fig. 5 is current-voltage (I-V) curve of testing the shown in Figure 3 pair of units in series optical-electric module that records.
Fig. 6 is based on the battery cascade module diagram of many carbon nano-tube, wherein: 1-carbon nano-tube, 2-palladium electrode, 3-scandium (or yttrium) electrode, 7-test electrode, the empty electrode pair of 8-.
Embodiment
Below by embodiment the present invention is described in further detail, but the scope that does not limit the present invention in any way.
Shown in Figure 3 is the citation form of tandem solar cell of the present invention.Between two on the semiconductive carbon nano tube asymmetrical outer electrodes 2 and 3, has an empty electrode pair every 1.5 microns, wherein electrode 2 is the about 0.6 micron palladium electrodes of width, electrode 3 is the about 0.6 micron scandium of width (or yttrium) electrodes, empty electrode pair 8 is made up of empty electrode of partly overlapping scandium (or yttrium) and the empty electrode of palladium, about respectively 0.6 micron of the width of the empty electrode of empty electrode of scandium (or yttrium) and palladium, about 0.3 micron of the width of overlapping region.Concrete preparation process is as follows:
1, obtains to be positioned at Si/SiO
2Intrinsic semiconductor carbon nano-tube (referring to Fig. 1) on the substrate;
2, the method by photoetching or electron beam lithography forms the pattern form of palladium electrode and the empty electrode of palladium on carbon nano-tube, evaporation layer of metal palladium then, and thickness is preferably more than 50 nanometers, peels off and removes unwanted metal level;
3, the method by photoetching or electron beam lithography forms the pattern form of scandium (or yttrium) electrode and the empty electrode of scandium (or yttrium) on carbon nano-tube, evaporation layer of metal scandium (or yttrium) then, and thickness is preferably more than 50 nanometers, peels off and removes unwanted metal level;
4, photoetching or electron beam lithography form the figure of encapsulated layer;
5, by ald (ALD) the mode one deck oxide parcel carbon pipe of growing, form encapsulated layer.
Backing material described in the above-mentioned steps 1 can be that silicon chip also can be other backing material, as glass etc.; Step 2 and 3 order can be changed mutually; The described oxide of step 5 can be logical luminescent material such as hafnium oxide, silica.
Based on said method, not only can make the multi-unit battery module of cascaded structure based on a carbon nano-tube, and as shown in Figure 6, can also make the battery module of series connection and parallel-connection structure based on many carbon nano-tube.
Though principle of the present invention and embodiment are that extinction and conductive channel material are set forth by carbon nano-tube, but those skilled in the art is to be understood that, technical scheme of the present invention is not limited to carbon nano tube device, be equally applicable to the photoelectric device based on other semiconductor nanowires, pipe, band (as the Graphene band), basic operation principle adapts to equally for other device based on the one dimension semiconductor nano material.Therefore, any modification or the improvement made on the basis of not departing from the present invention's spirit and essence all belong to category of the present invention, and protection scope of the present invention is decided on appended claims.
Claims (10)
1. tandem solar cell, as light absorbent and conductive channel, its two ends are asymmetric metal electrodes with the one dimension semiconductor nano material: an end is a palladium electrode, the other end is scandium or yttrium electrode; It is characterized in that, on the conductive channel between the described asymmetrical metal electrode, have n-1 empty electrode pair, conductive channel is divided into n the unit component that is cascaded, described empty electrode pair is made up of the empty electrode of palladium void electrode and scandium or yttrium that connects together, wherein the empty electrode of palladium is in close scandium or yttrium electrode one side, the empty electrode of scandium or yttrium is in close palladium electrode one side, and n is the positive integer greater than 1.
2. tandem solar cell as claimed in claim 1 is characterized in that, described one dimension semiconductor nano material is a carbon nano-tube.
3. tandem solar cell as claimed in claim 2 is characterized in that, described one dimension semiconductor nano material is the intrinsic semiconductor carbon nano-tube.
4. tandem solar cell as claimed in claim 2 is characterized in that, the conductive channel length of described unit component is 1～2 micron.
5. tandem solar cell as claimed in claim 1 is characterized in that, overlaps between empty electrode of the palladium in the described empty electrode pair and scandium or the empty electrode of yttrium.
6. the preparation method of arbitrary described tandem solar cell in the claim 1～5 comprises the steps:
1) method by photoetching or electron beam lithography forms the figure of palladium electrode and the empty electrode of palladium on the one dimension semiconductor nano material, and evaporation layer of metal palladium is peeled off and removed unwanted metal level then;
2) method by photoetching or electron beam lithography forms the figure of scandium or yttrium electrode and scandium or the empty electrode of yttrium on the one dimension semiconductor nano material, and evaporation layer of metal scandium or yttrium are peeled off and removed unwanted metal level then.
7. preparation method as claimed in claim 6 is characterized in that, step 1) and 2) in the metal layer thickness of institute evaporation be 50～100 nanometers.
8. preparation method as claimed in claim 6, it is characterized in that, in step 1) and 2) device is encapsulated after finishing: form the figure of encapsulated layer earlier by photoetching or electron beam lithography, one deck oxide of growing then wraps up device, perhaps utilizes organic encapsulating material to coat.
9. preparation method as claimed in claim 8 is characterized in that, described oxide is hafnium oxide or silica.
10. preparation method as claimed in claim 8 is characterized in that, described organic encapsulating material is a polymethyl methacrylate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102723348A (en) * | 2012-06-07 | 2012-10-10 | 北京大学 | Cascading infrared light detector based on semiconductor CNT (Carbon Nano Tube) |
| CN103681895A (en) * | 2013-11-28 | 2014-03-26 | 北京大学 | Infrared imaging detector based on carbon nano tubes and preparation method of detector |
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| CN101022137A (en) * | 2007-03-13 | 2007-08-22 | 上海交通大学 | One-dimensional nano-material-based photo-electric converter |
| CN101281933A (en) * | 2008-04-29 | 2008-10-08 | 北京大学 | Photoelectric device based on carbon nano-tube, optoelectronic integrated circuit unit and circuit |
| CN101960613A (en) * | 2008-03-07 | 2011-01-26 | 国立大学法人东北大学 | Photoelectric conversion element structure and solar battery |
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| US20060055392A1 (en) * | 2004-04-20 | 2006-03-16 | Passmore John L | Remotely communicating, battery-powered nanostructure sensor devices |
| CN101022137A (en) * | 2007-03-13 | 2007-08-22 | 上海交通大学 | One-dimensional nano-material-based photo-electric converter |
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| CN102723348A (en) * | 2012-06-07 | 2012-10-10 | 北京大学 | Cascading infrared light detector based on semiconductor CNT (Carbon Nano Tube) |
| CN103681895A (en) * | 2013-11-28 | 2014-03-26 | 北京大学 | Infrared imaging detector based on carbon nano tubes and preparation method of detector |
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