CN103489939A - Multi-junction heterogeneous quantum dot array and manufacturing method thereof and multi-junction heterogeneous quantum dot solar cell and manufacturing method thereof - Google Patents
Multi-junction heterogeneous quantum dot array and manufacturing method thereof and multi-junction heterogeneous quantum dot solar cell and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a multi-junction heterogeneous quantum dot array and a manufacturing method of the multi-junction heterogeneous quantum dot array. The multi-junction heterogeneous quantum dot array comprises silicon quantum dot layers and germanium quantum dot layers, the silicon quantum dot layers and the germanium quantum dot layers are arranged in a staggered mode. The multi-junction heterogeneous quantum dot array is simple in manufacturing technology, and can achieve industrialized production and reduce production cost effectively. The invention further discloses a multi-junction heterogeneous quantum dot solar cell made of the multi-junction heterogeneous quantum dot arrays and a manufacturing method of the multi-junction heterogeneous quantum dot solar cell. The multi-junction heterogeneous quantum dot solar cell mainly utilizes rich non-toxic and durable silicon as raw materials on the basis of a current silicon solar energy production line. After the method is performed according to the technical scheme, the conversion efficiency of solar chips will be increased in a breakthrough mode and is larger than 31%, the purpose that the production cost is reduced to be 0.5 dollar/watt is also achieved, and the electricity price holds the line with the power grid electricity prize.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of many knot hetero quntum point arrays and preparation method thereof and many knot hetero quntum point solar cells and preparation method thereof.
Background technology
Producing according to photon Gao Zhuan Change efficiency that the right hypothesis in pair of electrons are-hole calculates single crystal silicon at 1961 Shockley and Queisser is 31%.Up to the present, the laboratory Zhuan Change efficiency of single crystal silicon has reached 28.8%.Obviously, its development space is very limited.In order further to increase conversion efficiency, people have developed multijunction solar cell.It is a semi-conducting material with different energy gaps, by the size of band gap, is stacked from the top down, can absorb the photon of whole solar spectral.The laboratory Zhuan Change efficiency of III-V family semiconductor three-joint solar cell has reached 43.5% (theoretical value 48%).But production technology very complex and the production cost of this battery are very expensive, and required raw material are rare or harmful.These effects limit it at present only for space flight, military affairs with collect burnt system.
The another kind of method that increases conversion efficiency is to rely on quantum limitation effect to adjust semi-conductive band gap (Eg).Theory is calculated and experimental result all shows, and the band gap of silicon (Si) and germanium (Ge) quantum dot is greater than the body material, and their value depends on the size of quantum dot.For silicon quantum dot, when its diameter is reduced to 1nm from 5nm, corresponding band gap width Eg can be increased to 2eV from 1.1eV.And, for germanium quantum point, when its diameter is reduced to 2nm from 7nm, Eg is increased to 2eV from 0.6eV.As III-V family multijunction solar cell, people stack the quantum dot of different size to make many knot quantum dot solar cells together.Crucial technological challenge is that the distance between quantum dot need remain on 3nm guarantees charge carrier electrical conduction current then to get off.Except quantum dot can be adjusted band gap width, nearest theoretical research (in calendar year 2001) also shows that in quantum dot, the generation rate of many excitons is more than 2 times of body material.Many excitons refer to that a photon of absorption produces more than one electron-hole pair.The external quantum efficiency of internal authority Scientific Magazine report lead selenide quantum dot solar cell in 2011 has reached 114%.This just shows, the conversion efficiency of quantum dot solar cell can substantially exceed the conversion efficiency of body material.One is produced the silicon quantum dot method is to deposit substoichiometric silica (SiO with reactive evaporation
x, x<2) and silicon dioxide (SiO
2) multilayer film.SiO
xfilm occurs after annealing under 1100 ° of C being separated and causes the formation of quantum dot.In this way, the size of quantum dot and density can be controlled by adjusting silicon oxide layer thickness and forming x respectively.Afterwards, the method for this plane SH wave was also used substoichiometric germanium oxide (GeO
x) and SiO
2stacking generation Ge quantum dot.By the size of adjustment quantum dot and host material on every side, the band gap of germanium can be set between 0.66～2eV.Although obtained the quantum dot that is less than 5nm with such method common bluebeard.But distance between points still is greater than 3nm.Up to the present, seldom relevant for the acquisition spacing, be less than the report of 3nm quantum dot array.In addition, also there is the article report to use the method for Implantation Si ion implantation SiO
2film.In high annealing, silicon ion nucleation agglomerated together and form quantum dot.But the spacing between quantum dot is much larger than 3nm.This has hindered then leading effect and producing quite low short circuit current of the son that dams.Zhuan Change efficiency does not significantly increase.In addition, annealing temperature is higher than 1000 ° of C, and this is that photovoltaic industry is unacceptable.
Therefore, need a kind of new quantum dot array and preparation method thereof and many knot hetero quntum point solar cells and preparation method thereof to address the above problem.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of many knots hetero quntum point array that can adjust band gap and increase many excitons.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of many knot hetero quntum point arrays, comprise staggered silicon quantum dot layer and germanium quantum point layer.
Beneficial effect: many knot hetero quntum point arrays of the present invention can be adjusted band gap by staggered silicon quantum dot layer and germanium quantum point layer, increase the generation of many excitons by staggered silicon quantum dot layer and germanium quantum point layer.
Preferably, in described quantum dot array, between quantum dot, isolate, the distance between quantum dot and quantum dot is 0.5-3nm.Above-mentioned quantum dot array has increased bandgap range than pure silicon quantum dot array: from 0.6eV to 2eV (the pure silicon quantum is from 1.1eV to 2eV).This has comprised most sunlight frequency spectrum, and the photon from utilized most sunlight frequency spectrum and the generation aspect of many excitons have increased conversion efficiency.
The technical problem that the present invention also will solve is to provide the preparation method of above-mentioned many knot hetero quntum point arrays.
The preparation method of above-mentioned many knot hetero quntum point arrays comprises the following steps:
(1) prepare a substrate, the thickness of described substrate is 20 ~ 180um;
(2) preparation Si/Ge multilayer superlattice on the substrate of step (1), wherein, the gross thickness of described Si/Ge multilayer superlattice is 50 ~ 400nm, the protective layer that described Si/Ge multilayer superlattice comprise silicon layer and the germanium layer of alternative arrangement and are positioned at the last layer of described Si/Ge multilayer superlattice, the thickness of described silicon layer and described germanium layer is 2 ~ 10nm, and the thickness of described protective layer is 10 ~ 30nm;
(3) described substrate and described Si/Ge multilayer superlattice are carried out to oxidation simultaneously, described oxidizing temperature is that 200 ~ 700 ° of C and oxidization time are 5 ~ 30 minutes, and the silicon layer of described alternative arrangement and germanium layer all form quantum dot film, obtains many knot hetero quntum point arrays.
Preferably, the Si/Ge multilayer superlattice described in step 2 are obtained by epitaxial growth method, plasma enhanced chemical vapor deposition method, evaporation or magnetically controlled sputter method.The preparation method is simple, and selectable implementation method is more.
Step is oxidized to wet oxidation or dry oxidation described in (3), and wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes.
Preferably, described substrate is silicon substrate, germanium substrate, glass substrate or organic plastics film-substrate.
Preferably, described protective layer is silicon protective layer or silicon nitride protective layer.
Beneficial effect: preparation method's technique of many knot hetero quntum point arrays of the present invention is simple, and process conditions are easy to control.From the generation temperature that reduces quantum dot with do not increase the equipment aspect and reduced production cost.
Technical problem: the technical problem that the present invention also will solve is to provide a kind of many knot hetero quntum point solar cells, to overcome larger problem and the too high problem of pure silicon quantum dot formation temperature of distance between the pure germanium quantum dot.
Technical scheme: for solving the problems of the technologies described above, the technical scheme that many knot hetero quntum point solar cells of the present invention adopt is as follows:
A kind of many knot hetero quntum point solar cells; comprise successively from top to bottom rear electrode, substrate, Si/Ge quantum dot layer, protective layer and front electrode; described Si/Ge quantum dot layer is the formation that is staggered of silicon quantum dot layer and germanium quantum point layer; described protective layer thickness is 10 ~ 30nm; in described Si/Ge quantum dot layer, between quantum dot, isolate, the distance between quantum dot and quantum dot is 0.5-3nm.
Preferably, described substrate is silicon substrate, germanium substrate, glass substrate or organic plastics film-substrate.
Preferably, described rear electrode is aluminium electrode, copper electrode, graphite electrode, steel electrode, cast iron electrode or tungsten alloy electrode.
Preferably, the indium tin oxide film electrode that described front electrode is conductive, transparent or graphene membrane electrode (as protective layer is silicon nitride, first go it, then do front electrode).
Preferably, described protective layer is silicon protective layer or silicon nitride protective layer.
Beneficial effect: it is primary raw material that many knot hetero quntum point solar cells of the present invention mainly be take nontoxic durable abundant crystal silicon, and can current silicon solar production line be basic.Many knot hetero quntum point solar cells of the present invention, the band gap of Si/Ge quantum dot layer is adjustable in 0.6eV arrives the scope of 2eV.In the conversion efficiency and band gap graph of a relation of calculating at Shockley and Queisser, the area of a polygon of its correspondence is greater than 50% with the ratio of the gross area.Therefore the theoretical maximum conversion efficiency of the heterogeneous quantum solar cell of many knots of the present invention will be greater than 50%.In addition, the preparation method of Si/Ge quantum dot layer of the present invention is simple, and the generation temperature of quantum dot is lower, and can prepare on the existing equipment basis, does not need increase equipment.Can effectively reduce production costs.
Technical problem: the technical problem that the present invention also will solve is to provide a kind of preparation method of many knot hetero quntum point solar cells.
Technical scheme: for solving the problems of the technologies described above, the technical scheme that the preparation method of many knot hetero quntum point solar cells of the present invention adopts is as follows:
The preparation method of many knot hetero quntum point solar cells as above, is characterized in that, comprises the following steps:
(1), prepare a substrate, the thickness of described substrate is 20 ~ 180um;
(2), preparation Si/Ge multilayer superlattice on the substrate of step (1), wherein, the gross thickness of described Si/Ge multilayer superlattice is 50 ~ 400nm, the protective layer that described Si/Ge multilayer superlattice comprise silicon layer and the germanium layer of alternative arrangement and are positioned at the last layer of described Si/Ge multilayer superlattice, the thickness range of described silicon layer and described germanium layer is between 2 ~ 10nm, and the thickness of described protective layer is 10 ~ 30nm;
(3) described substrate and described Si/Ge multilayer superlattice are carried out to oxidation simultaneously, wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes, and the silicon layer of described alternative arrangement and germanium layer all form quantum dot film, obtains many knot hetero quntum point arrays;
(4) substrate one side at described many knot hetero quntum point arrays arranges rear electrode;
(5) electrode before protective layer one side of described many knot hetero quntum point arrays arranges.Preferably, the Si/Ge multilayer superlattice described in step (2) are obtained by epitaxial growth method, plasma enhanced chemical vapor deposition method, evaporation or magnetically controlled sputter method.
Preferably, step is oxidized to wet oxidation described in (3), and wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes.
Beneficial effect: the many knots hetero quntum point solar cell that utilizes this method to prepare, in the Si/Ge quantum dot layer, between quantum dot, isolate, distance between quantum dot and quantum dot is 0.5-3nm, and the band gap of Si/Ge quantum dot layer is in 0.6eV arrives the scope of 2eV.In the conversion efficiency and band gap graph of a relation of calculating at Shockley and Queisser, the area of a polygon of its correspondence is greater than 50% with the ratio of the gross area.The theoretical maximum conversion efficiency of the heterogeneous quantum solar cell of many knots that therefore utilizes this method to prepare will be greater than 50%.In addition, the preparation method of Si/Ge quantum dot layer of the present invention is simple, and the generation temperature of quantum dot is lower, and can prepare on the existing equipment basis, does not need increase equipment.Can effectively reduce production costs.
The accompanying drawing explanation
Fig. 1 is the schematic diagram of silicon substrate;
Fig. 2 is the schematic diagram of growth Si/Ge superlattice on silicon substrate;
Fig. 3 is the schematic diagram of many knot hetero quntum point arrays;
Fig. 4 is the schematic diagram that is provided with many knots hetero quntum point array of front electrode;
Fig. 5 is the schematic diagram of many knot hetero quntum point solar cells;
Fig. 6 is conversion efficiency and the band gap graph of a relation that Shockley and Queisser calculates;
Fig. 7 be various different band gap semiconductor materials under the body state and the quantum dot state under the energy conversion efficiency curve;
Fig. 8 is silicon quantum dot layer of experimental example and the transmission electron microscope picture of the staggered quantum dot array of germanium quantum point layer;
Fig. 9 is the graph of a relation of oxidated layer thickness and oxidization time.
Embodiment
Refer to shown in Fig. 1, many knot hetero quntum point arrays of the present invention comprise staggered silicon quantum dot layer and germanium quantum point layer.Wherein, in quantum dot array, between quantum dot, isolate, the distance between quantum dot and quantum dot is 0.5-3nm.Many knot hetero quntum point arrays can be adjusted band gap by staggered silicon quantum dot layer and germanium quantum point layer, increase the generation of many excitons by staggered silicon quantum dot layer and germanium quantum point layer.Increased bandgap range than pure silicon quantum dot array: from 0.6eV to 2eV (the pure silicon quantum is from 1.1eV to 2eV).This has comprised most sunlight frequency spectrum, and the photon from utilized most sunlight frequency spectrum and the generation aspect of many excitons have increased conversion efficiency, thereby makes the theoretical transformation efficiency of this solar energy to surpass 50%.The preparation method of many knot hetero quntum point arrays of the present invention comprises the following steps: at first utilize a silicon substrate, it is also N-shaped of p-type, and its thickness is between 20 to 180 μ m.Because the absorption coefficient of germanium is larger than silicon, it requires lower absorber thickness.In addition, also germanium substrate, glass substrate or organic plastics film-substrate of substrate.
Refer to shown in Fig. 2 preparation Si/Ge multilayer superlattice on silicon substrate.The gross thickness of superlattice at 50nm between 400nm.The available general thin film technique of the production of superlattice, as epitaxy, plasma enhanced chemical vapor deposition method (PECVD), the methods such as evaporation and magnetron sputtering.The thickness of each layer is in 2 ~ 10nm, with broad film after guaranteeing oxidation, becomes quantum dot.In the preparation of Si/Ge multilayer superlattice, the thickness of silicon layer and germanium layer can equate, but also do not wait.Be greater than silicon layer thickness as the thickness of germanium layer; In superlattice, the thickness of all silicon layers or germanium layer equates, but also do not wait.As be thinner than near substrate away from substrate.But the thickness of silicon layer and the thickness of germanium layer can be in the desired amount the son point size and determine.Preferably, the thickness of silicon layer and germanium layer is all 5nm, just can realize that in this case spacing between quantum dot is less than the target of 3nm.Last layer is protective layer, can be silicon protective layer or silicon nitride protective layer, and its thickness requirement is at 10 ~ 30nm.This layer has two effects: the one, and in the oxidizing process of back, protect more broad superlattice complete by complete oxidation.It two is contact zones (with reference to Fig. 2) of the emitter for making solar cell.
Refer to shown in Fig. 3, substrate and superlattice are carried out to oxidation together.In the process of preparation Si/Ge superlattice, the defect of Si and Ge film interface is Si0
2formation vantage point is provided.SiO in oxidizing process
2to preferentially form in these positions, it vertically separates the Si film with the Ge film.Again due to the Si film and the Ge film very thin, in deposition process, they do not form the film of two dimension uniformly, but form closelypacked quantum dot film.SiO in oxidizing process
2closelypacked quantum dot laterally is divided into to independently quantum dot, can obtains thus many knot hetero quntum point arrays of the present invention.
Refer to shown in Fig. 5; utilize the above-mentioned many knots of many knots hetero quntum point array preparation hetero quntum point solar cell; many knot hetero quntum point solar cells comprise rear electrode, substrate, Si/Ge quantum dot layer, protective layer and front electrode from top to bottom successively; the Si/Ge quantum dot layer is the formation that is staggered of silicon quantum dot layer and germanium quantum point layer; but protective layer silicon protective layer; also silicon nitride protective layer; its thickness is 10 ~ 30nm; in the Si/Ge quantum dot layer, between quantum dot, isolate, the distance between quantum dot and quantum dot is 0.5-3nm.。
The preparation method of above-mentioned many knot hetero quntum point solar cells, on the basis of the many knots hetero quntum point array obtained, carries out the preparation of p-n junction.If the substrate of selecting is p-type, Si/Ge quantum dot layer and protective layer are answered the N-shaped doping.Otherwise, if the substrate of selecting is N-shaped, Si/Ge quantum dot layer and protective layer are answered the p-type doping.The method of doping can, with Implantation or thermal diffusion etc., also can synchronously be carried out in deposition process.
Refer to shown in Fig. 4, front electrode can be with the indium tin oxide film (ITO) of conductive, transparent, also available Graphene, and it is the two-dimensional structure of carbon.The thickness of this graphene conductive film only has 0.335 nanometer.Its resistivity is roughly the same with the ITO used at present, but its transmissivity is far above ITO (Graphene is 97.4%, and ITO is 90%).Particularly, the raw material of Graphene is graphite, its available chemical vapour deposition technique and preparing;
Refer to shown in Fig. 5 aluminium, copper, graphite, steel, cast iron or the tungsten alloy electrode that rear electrode can be commonly used by photovoltaic industry or the preparation of other cheap metal material material; Be preferably the aluminium electrode.
By many knot band theories (energy band engineering), the theoretical maximum conversion efficiency of the many knots of prediction hetero quntum point solar cell.Refer to shown in Fig. 6, Shockley and Queisser represents the theoretical maximum conversion efficiency by the size of area.They are normalized to one to the gross area.As the Eg=1.1eV of single crystal silicon, its corresponding rectangular area is 31% with the ratio of the gross area.So theoretical maximum conversion efficiency 31% of single crystal silicon.The band gap of the heterogeneous quantum of many knots of the present invention is at 0.6eV in the scope of 2eV, and the area of a polygon of its correspondence is greater than 50% with the ratio of the gross area.This theoretical maximum conversion efficiency that just shows the heterogeneous quantum solar cell of many knots will be greater than 50%.This step can be by using the regulation and control that realize band gap from being thinned to thick superlattice.
Refer to shown in Fig. 7, press quantum dot theoretical (quantum limitation effect), the theoretical maximum conversion efficiency of the many knots of prediction hetero quntum point solar cell.Fig. 7 be the various different band gap semiconductor materials that calculate of Beard group under the body state and the energy under the quantum dot state change efficiency.Curve 1 is that the hypothesis photon energy produces many excitons to greatest extent; Curve 2 is that the photon energy that hypothesis only has energy to be greater than 2Eg produces two pairs of electron-hole pairs; Curve 3 is that the photon energy that hypothesis only has energy to be greater than 2.5Eg produces two pairs of electron-hole pairs; The like.Curve 6 is body material theoretical maximum conversion efficiencies of calculating according to the theory of Shockley and Queisser.As can be seen from Figure 7, concerning silicon (Eg=1.1eV), the theoretical maximum conversion efficiency of body material is 31%; The theoretical maximum conversion efficiency of quantum dot is 42%, even the photon that is greater than 2Eg at energy could produce under the condition of two pairs of electron-hole pairs, the theoretical transformation efficiency of quantum dot also reaches 36%.In addition, from the phonon engineering, by three kinds of materials (Si, Ge SiO
2) optical crystal that forms, there is phonon band gap and the slow characteristics such as mobility.These make hot carrier (by energy, being greater than the photon of Eg and the charge carrier that produces) in the competition that turns cold or double, and the hot carrier multiplication is won victory.In other words, the speed that turns cold of hot carrier greatly reduces in the hetero quntum point array.
Refer to shown in Fig. 8, the experimental example of the hetero quntum point of knot more than array: Fig. 8 is the transmission electron microscope picture of a silicon quantum dot layer and the staggered quantum dot array of germanium quantum point layer.Its preparation technology is as follows: on a p-type silicon wafer by epitaxially grown method growth superlattice Si/Ge/Si(20/20/20nm).The epitaxial growth method superlattice of growing for this experimental example are in order to have guaranteed repeatability.Can also pass through film deposition techniques cheaply and replace it.Then carry out wet oxidation.In this step, silicon quantum dot and germanium quantum point are with regard to self-assembling formation.As can be seen from Figure 8: the thickness of silicon dioxide is about 3nm.This is for the clearly interval between observation of quantum point and quantum dot, the higher oxidizing temperature of this experimental example (700 ° of C) and longer oxidization time (75 minutes).But they can be correspondingly reduced to be less than the target of 3nm.Fig. 9 is the thickness of silicon dioxide in wet oxidation process that utilizes the SILVACO software simulation.Fig. 9 has provided under different temperatures, the relation of oxidated layer thickness and oxidization time.As shown in the figure, if keep oxidizing temperature constant (700 ° of C), oxidization time reduced to 10 minutes from 75 minutes, and oxidated layer thickness will drop to 1nm.In Fig. 8, the diameter of silicon quantum dot is 4.5nm.It can reduce by the original thickness of further minimizing silicon layer.The size of germanium quantum point and the original thickness of germanium film are unanimous on the whole.Because silicon dioxide has a less Gibbs free energy than germanium dioxide, generate silicon dioxide so silicon materials are at first oxidized.
In sum, the manufacture craft of many knot hetero quntum point arrays of the present invention is simple, easy to control.The silicon and the staggered quantum dot array of germanium that produce in this way, than pure germanium quantum dot array, the distance between quantum dot greatly reduces.Because in the present invention, need to be at two-layer GeO
xbetween add SiO
2layer, this makes the distance between quantum dot be less than 3nm.Thereby increased and then led effect and short circuit current.Than pure silicon quantum dot array, the formation temperature of quantum dot is low, is less than 700 ° of C, and this has correspondingly reduced industrial cost.The preparation of the quantum dot array that silicon and germanium are staggered does not need to increase any equipment investment, and available same equipment is as PECVD.Silicon and germanium belong to same gang element, do not have any pollution problem in production, with the silicon technology compatibility.The most important thing is the quantum dot array that silicon and germanium are staggered, increased bandgap range than pure silicon quantum dot array, from 0.6eV to 2eV.This has comprised most sunlight frequency spectrum, thereby makes the theoretical transformation efficiency of this solar energy to surpass 50%.The advantage of this array is: from the generation temperature that reduces quantum dot with do not increase the equipment aspect and reduced production cost; Photon from utilized most sunlight frequency spectrum and the generation aspect of many excitons have increased conversion efficiency.
Many knot hetero quntum point solar cells simultaneously of the present invention mainly be take nontoxic durable abundant silicon as raw material and be take current silicon solar production line as basis.After carrying out according to this programme, the conversion efficiency of solar chip will have breakthrough increase, and conversion efficiency is greater than 31%, and can realize that production cost is reduced to the target of 0.5 dollar/watt, and this electricity price and electrical network electricity price maintain an equal level.
Claims (15)
1. the hetero quntum point of knot more than kind array, is characterized in that, comprises staggered silicon quantum dot layer and germanium quantum point layer.
2. many knot hetero quntum point arrays as claimed in claim 1, is characterized in that, in described quantum dot array, between quantum dot, isolate, the distance between quantum dot and quantum dot is 0.5-3nm.
3. the preparation method of many knot hetero quntum point arrays as described as claim 1-2, is characterized in that, comprises the following steps:
(1), prepare a substrate, the thickness of described substrate is 20 ~ 180um;
(2), preparation Si/Ge multilayer superlattice on the substrate of step (1), wherein, the gross thickness of described Si/Ge multilayer superlattice is 50 ~ 400nm, the protective layer that described Si/Ge multilayer superlattice comprise silicon layer and the germanium layer of alternative arrangement and are positioned at the last layer of described Si/Ge multilayer superlattice, the thickness range of described silicon layer and described germanium layer is between 2 ~ 10nm, and the thickness of described protective layer is 10 ~ 30nm;
(3) described substrate and described Si/Ge multilayer superlattice are carried out to oxidation simultaneously, wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes, and the silicon layer of described alternative arrangement and germanium layer all form quantum dot film, obtains many knot hetero quntum point arrays.
4. the preparation method of many knot hetero quntum point arrays as claimed in claim 3, it is characterized in that, the Si/Ge multilayer superlattice described in step (2) are obtained by epitaxial growth method, plasma enhanced chemical vapor deposition method, evaporation or magnetically controlled sputter method.
5. the preparation method of many knot hetero quntum point arrays as claimed in claim 3, is characterized in that, step is oxidized to wet oxidation or dry oxidation described in (3), and wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes.
6. the preparation method of many knot hetero quntum point arrays as claimed in claim 3, is characterized in that, described substrate is silicon substrate, germanium substrate, glass substrate or organic plastics film-substrate.
7. the preparation method of many knot hetero quntum point arrays as claimed in claim 3, is characterized in that, described protective layer is silicon protective layer or silicon nitride protective layer.
8. tie the hetero quntum point solar cell one kind more; it is characterized in that: comprise successively from top to bottom rear electrode, substrate, Si/Ge quantum dot layer, protective layer and front electrode; described Si/Ge quantum dot layer is the formation that is staggered of silicon quantum dot layer and germanium quantum point layer; the thickness of described protective layer is 10 ~ 30nm; in described Si/Ge quantum dot layer, between quantum dot, isolate, the distance between quantum dot and quantum dot is 0.5-3nm.
9. many knot hetero quntum point solar cells as claimed in claim 8, is characterized in that, described substrate is silicon substrate, germanium substrate, glass substrate or organic plastics film-substrate.
10. many knot hetero quntum point solar cells as claimed in claim 8, is characterized in that, described rear electrode is aluminium electrode, copper electrode, graphite electrode, steel electrode, cast iron electrode or tungsten alloy electrode.
11. many knot hetero quntum point solar cells as claimed in claim 8, is characterized in that indium tin oxide film electrode or graphene membrane electrode that described front electrode is conductive, transparent.
12. many knot hetero quntum point solar cells as claimed in claim 8 is characterized in that described protective layer is silicon protective layer or silicon nitride protective layer.
13. the preparation method of many knot hetero quntum point solar cells as described as claim 8-12 any one, is characterized in that, comprises the following steps:
(1) prepare a substrate, the thickness of described substrate is 20 ~ 180um;
(2) preparation Si/Ge multilayer superlattice on the substrate of step (1), wherein, the gross thickness of described Si/Ge multilayer superlattice is 50 ~ 400nm, the protective layer that described Si/Ge multilayer superlattice comprise silicon layer and the germanium layer of alternative arrangement and are positioned at the last layer of described Si/Ge multilayer superlattice, the thickness range of described silicon layer and described germanium layer is 2 ~ 10nm, and described protective layer thickness is 10 ~ 30nm;
(3) described substrate and described Si/Ge multilayer superlattice are carried out to oxidation simultaneously, wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes, and the silicon layer of described alternative arrangement and germanium layer all form quantum dot film, obtains many knot hetero quntum point arrays;
(4) substrate one side at described many knot hetero quntum point arrays arranges rear electrode;
(5) electrode before protective layer one side of described many knot hetero quntum point arrays arranges.
14. the preparation method of many knot hetero quntum point solar cells as claimed in claim 13, is characterized in that step
(2) the Si/Ge multilayer superlattice described in are obtained by epitaxial growth method, plasma enhanced chemical vapor deposition method, evaporation or magnetically controlled sputter method.
15. the preparation method of many knot hetero quntum point solar cells as claimed in claim 13 is characterized in that step is oxidized to wet oxidation or dry oxidation described in (3), wherein, oxidizing temperature is 200 ~ 700 ° of C, and oxidization time is 5 ~ 30 minutes.
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