CN102738259A - Multiband semiconductor compositions for photovoltaic devices - Google Patents

Multiband semiconductor compositions for photovoltaic devices Download PDF

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CN102738259A
CN102738259A CN2012102265879A CN201210226587A CN102738259A CN 102738259 A CN102738259 A CN 102738259A CN 2012102265879 A CN2012102265879 A CN 2012102265879A CN 201210226587 A CN201210226587 A CN 201210226587A CN 102738259 A CN102738259 A CN 102738259A
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alloy
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semiconductor
oxygen
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弗拉迪斯劳·瓦卢克维兹
于金曼
吴俊乔
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University of California
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0304—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
    • H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0693—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells the devices including, apart from doping material or other impurities, only AIIIBV compounds, e.g. GaAs or InP solar cells
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Abstract

The invention provides multiband semiconductor compositions for photovoltaic devices. The highly mismatched alloy Znl-yMnyOxTe1-x- 0<=y<l and O<x<1 and other Group II-IV-Oxygen implanted alloys have been synthesized using the combination of oxygen ion implantation and pulsed laser melting. Incorporation of small quantities of isovalent oxygen leads to the formation of a narrow, oxygen-derived band of extended states located within the band gap of the Znl-yMnyTe host. With multiple band gaps that fall within the solar energy spectrum, Znl-yMnyOxTel1-x is a material perfectly satisfying the conditions for single junction photovoltaics with the potential for power conversion efficiencies surpassing 50%.

Description

The multiband semiconductor compositions that is used for photovoltaic device
The application is to be denomination of invention the dividing an application for " multiband semiconductor compositions that is used for photovoltaic device " No. 200480035510.7 applications on November 29th, 2004 applying date.
About the research of supporting in the federal scope or the statement of exploitation
Here describe and the invention of prescription has partly utilized the subsidy of the fund that USDOE provides according to the DE-AC03-76SF000-98 contract signed between USDOE and Univ California.Government has certain right to the present invention.
Technical field
The present invention relates to be used for the new material of photovoltaic device, more specifically relate to the multiband semiconductor that is used for the high-energy conversion efficiency solar cell.
Background technology
The various materials that are suitable for photovoltaic device are well-known; For example tetrahedral amorphous semiconductor (for instance; Amorphous silicon, amorphous silicon germanium and noncrystalline silicon carbide) and comprise IV family (Si), II-VI compound semiconductor (for instance; CdTe) and the polycrystalline and the single crystal semiconductor of III-V compound semiconductor (GaAs, GaInP, GaAlAs for instance).Traditional solar cell uses through foreign ion injection or thermal diffusion are tied to the monocrystalline matrix of silicon (Si) or GaAs (GaAs) or through the pn that the epitaxial growth of impurity doped layer on this monocrystalline matrix forms.Yet this unijunction solar cell only has limited efficient, and this is because they all are responsive to the limited part of whole solar spectrums.Tie and to raise the efficiency through using with the formed a large amount of p/n of semiconductors that have the responsive different ability bands of the different piece of solar spectrum.This notion is at many knots or tandem solar cell (J.M.Olson, T.A.Gessert, M.M.AlJasim, Proc.18 ThIEEE Photovoltaic Specialists Conference, 552, Las Vegas, Oct.21-25,1985, its full content is incorporated this paper into as a reference) as being achieved in GaAs/GInP binode or Ge/GaAs/GaInP three junction batteries.In the most advanced type of this battery, reached 37% energy conversion efficiency.The complexity and the high manufacturing cost of design have limited the application (M.Yamaguchi, Solar Energy Mat.& Solar Cells, 75,261 (2003)) of this battery on space technology.
Other improves the method for solar battery efficiency based on the notion of multiband semiconductor (M.Wolf, Proc.IRE, 48,1246 (1960) and A.Luque, A.Marti., Phys.Rev.Lett., 78,5014 (1997)).People suppose, can use one to have a plurality of absorptions and replace using several semiconductors with different band gap from the semiconductor of the absorption edge of solar spectrum different piece photon.The most important advantage of this design of high efficiency solar cell is that their only need a single p/n knot, thereby simplifies battery design greatly and reduce production costs.Predict to have in the solar cell of material manufacturing of three and four ability bands of optimization in theory, can obtain desirable energy conversion efficiency respectively up to 63% and 72% in use.
The actual realization that can be used in the multiband semiconductor of solar cell is quite difficult.Once there were some to be out for introducing the impurity or the defective that can in the band gap of standard semiconductor such as Si or GaAs, form extra arrowband of big concentration.These effort are success not, because impurity and defective have changed the crucial electrical property of material, thereby can not make the solar cell of operate as normal.Also there is not the demonstration of attested solar cell based on the notional work of multiband semiconductor up to now.
Occurred one type of new semiconductor in recent years, its key property is through being replaced the host atoms of relative fraction and modification greatly by unusual different electronegative element, and it is called high mispairing alloy (HMAs).Wherein V family anion is by the substituted III-V alloy of N part of equal value [Semiconductor Science and Technology 17,2002, Special Issue:III-N-V semiconducting alloy; Its full content is incorporated this paper into as a reference] or wherein VI family anion by the substituted II-VI alloy of O part [K.M.Yu, W.Walukiewicz, J.Wu; J.W.Beeman, J.W.Ager, E.E.Haller; I.Miotkowski, A.K.Ramdas and P.Becla, Appl.Phys.Lett.80; 1571 (2002), its full content is incorporated this paper into as a reference] be the example of well-known HMA.For example, when just 1% As atom is replaced by N, GaN xAs 1-xThe band gap that shows strong 180meV reduces.Predicted and that through experimental demonstration the electronics band structure of this HMA is by [W.Walukiewicz, W.Shan, the K.M.Yu of determining that interact of the anti-cross between the extended state of fixing O or N attitude and semiconductor substrate; J.W.Ager III, E.E.Haller, I.Miotlowski; M.J.Seong, H.Alawadhi, A.K.Ramdas; Phys.Rev.Lett.85,1552 (2000), its full content is incorporated this paper into as a reference].Reciprocation is divided into conduction band the sub-band of two non-parabola shapes: E +And E -
Summary of the invention
The invention provides one type of new multiband gap semiconductor material.This type multiband material can be used for the design of high efficiency solar cell.In one embodiment, comprise the II-VI compound semiconductor according to material of the present invention, wherein the atom of sub-fraction VI family is replaced formation II-O by oxygen atom x-VI 1-xAlloy.In one embodiment, can use ion to inject and then come manufactured materials through pulse laser fusion and/or thermal annealing.In another embodiment, material also can be used as epitaxial film and utilizes pulsed laser deposition and comprise molecular beam epitaxy and the various epitaxial growth technologies of organometallic chemistry gas deposition and synthesizing.In one embodiment, in above-mentioned material, make solar cell through forming a single p/n knot.
Description of drawings
Back through together with accompanying drawing is described in detail, can understand the present invention at an easy rate:
Fig. 1 is 3.3%O +The Zn that injects 0.88Mn 0.12The Te sample is then at 0.04-0.3J/cm 2A series of light modulation reflectivity (PR) spectrum that is obtained by the pulse laser fusion under the energy fluence that increases.Also listed the Zn that is in growth conditions among the figure 0.88Mn 0.12The PR spectrum of Te crystal is to be used for comparison.Can observe two absorption edges of conduction band edge from the valence band edge to the lower floor and the upper strata, explain to have formed an other conduction band.
Fig. 2 is 3.3%O +The Zn that injects 0.88Mn 0.12The Te sample is 0.15J/cm in fluence 2PLM after then under the temperature between 300 and 700 ℃, carry out the RTA in 10 seconds and a series of PR spectrum that obtains.
Fig. 3 is the Zn of different x values 0.88Mn 0.12O xTe 1-xThe E of alloy -And E +Energy position.
Fig. 4 has represented the Zn of x～0.02 with sketch map 0.88Mn 01.2O xTe 1-xOptical transition between middle different can being with.The band structure that calculates (left side section) and the density of states (right section).The right section of figure has shown three possible optical transitions.(higher) energy peak lower among Fig. 1 is corresponding to E V-(E V+) transition.
Fig. 5 is volt-ampere (I/V) characteristic curve of the p type p/n that on multiband semiconductor, makes knot and the spectrum relation curve of photovoltage (PV).Knot is by the p type Zn that injects with O and Cl ion 0.88Mn 0.12The Te matrix is formed.The implanted layer on top is by the pulse laser fusion.The O atomic component replaces the Te atom and forms other conduction band.The Cl ion replaces the Te atom and provides the n type to mix.Between p mold base and n type top layer, form the p/n knot.
Fig. 6 be calculate by 3-frequency band Zn 0.88Mn 0.12O xTe 1-xAlloy is with the energy conversion efficiency of the solar cell of the variation manufacturing of O content.Solid line is the experience fitting of a polynomial of calculated data.
Fig. 7 is GaN xAs 1-x-yP yIn with respect to conduction band energy minimum value E ΓAnd E XThe nitrogen energy be E NThe position of energy level.
Fig. 8 is GaN xAs 1-x-0.6P 0.4In above conduction band E +With middle E -The relation curve of the energy of conduction band and N content x.
Embodiment
To specify specific embodiments more of the present invention now.Illustrate the embodiment of these specific embodiments in the accompanying drawings.When describing together with these specific embodiments when of the present invention, be appreciated that to being not to limit the invention to described embodiment.On the contrary, it will comprise like what the accessory claim book was limited and comprise alternatives, change and equivalence within the spirit and scope of the present invention.In the following description, set forth many details and understood fully of the present invention so that provide.Lack these some or all of details and also can put into practice the present invention.In other cases, do not describe well-known process operation in detail, this is not for the present invention is unnecessarily covered.For the purpose of all purposes, the full content of whole lists of references of being quoted here specially here is cited as reference.
In this specification and additional claims, only if extra clearly regulation done in context, otherwise singulative also comprises the plural form of mentioned content.Only if otherwise provide, otherwise employed here all technical scientific terms and those skilled in the art common understand have a same implication.
In one embodiment of the invention, disclose a kind of semiconductor composition that comprises ternary or quaternary alloy, said alloy comprises II family element, VI family element, oxygen and optional the third element " A ", and wherein said alloy has (II family) (1-y)(A) yO x(VI family) (1-x)Molar fraction form, and 0≤y＜1,0＜x＜1, " A " comprises magnesium.In one embodiment, a kind of Zn of comprising is disclosed 0.88A 0.12O xTe 1-xAlloy, 0＜x＜0.05 wherein.Preferably, x is between about 0.01 and 0.05.
In another embodiment, a kind of Cd has been proposed 1-yMg yO xTe 1-xAlloy, 0＜y＜1 and 0＜x＜0.05, preferably, x is between about 0.01 and 0.05.
In yet another embodiment of the present invention, disclose a kind of semiconductor composition that comprises ternary or quaternary alloy, said alloy comprises II family element, VI family element, oxygen and optional the third element " A ", and wherein said alloy has (II family) (1-y)(A) yO x(VI family) (1-x)Molar fraction form, 0≤y＜1,0＜x＜0.05, " A " is made up of manganese or magnesium, and wherein II family element does not comprise cadmium.Preferably, x is between about 0.01 and 0.05.
In another embodiment of the present invention; A kind of semiconductor composition and their application in photovoltaic device that comprises ternary or quaternary alloy disclosed; Said alloy comprises II family element, optional another kind II family's element " A "; S or Se, oxygen and tellurium composition, wherein said alloy have (II family) (x)(A) (1-x)(S or Se) (1-y-z)(Te) (y)(O) (z)Molar fraction form and 0＜x≤1,0＜z＜0.10,0＜y＜0.2.The notion that is used for the multiband material of photovoltaic application can expand to four bands of ZnSeOTe alloy, wherein forms be positioned near what the band of valence band and another one with O be correlated with relevant with Te of two additional bands, and is positioned at the band near conduction band.In a preferred embodiment of the invention, Zn is provided xMn 1-xSe (1-y-z)Te yO zAlloy, wherein 0＜x≤1,0＜z＜0.04 and 0＜y＜0.2.
In yet another embodiment of the present invention, disclose a kind of semiconductor composition that comprises alloy, said alloy comprises GaN xAs 1-x-yP y, 0.3≤y＜0.5 and 0＜x＜0.05 wherein.
In another embodiment of the present invention, a kind of semiconductor composition that comprises alloy is disclosed, said alloy comprises Ga 1-yIn yN xP 1-x, wherein 0.4≤y＜0.6, and 0＜x＜0.05.
In yet another embodiment of the present invention, x is between about 0.02 and 0.04.
In yet another embodiment of the present invention, x is between about 0.01 and 0.05.
In yet another embodiment of the present invention, z is between about 0.01 and 0.04.
In yet another embodiment of the present invention, z is between about 0.02 and 0.04.
In yet another embodiment of the present invention, 0.01≤x≤0.04.
In yet another embodiment of the present invention, 0.02≤x≤0.03.
In yet another embodiment of the present invention, 0.01≤x≤0.04.
All compositions disclosed herein all are suitable for being used for the film of photovoltaic device.
With regard to " II-VI family " compound and their alloy, it means other binary, ternary and the quaternary alloy of each family's element of the compound semiconductor materials that comprises all compositions such as ZnTe, CdTe and all.II family element comprises Mn, Mg, Zn and Cd.VI family element comprises O, S, Se and Te.Iii group element comprises B, Al, Ga, In and Tl.V group element comprises N, P, As and Sb.
It is understandable that, the present invention includes (being pure intrinsic semiconductor) doping or non-doping and can arrange to form the various semi-conducting materials that have such as the semiconductor device of the knot of pn, pnp, npn, pin, pip etc.In certain embodiments, material can be doped in a conventional manner.For example, can use dopant commonly used for example B, P, As, In and Al.Dopant can be selected from II, III, IV, V, VI isofamily.
As a non-restrictive example of one embodiment of the invention, the O of use 90 and 30keV +Carry out a plurality of energy and be injected into Zn 1-yMn yTo form the thick layer of about 0.2 μ m, it has constant relatively O concentration with respect to the O molar fraction of 0.0165-0.044 in Te (y=0 and the 0.12) monocrystalline.Be noted that the present invention proposes to replace Mn with Mg.With O +The sample that injects uses the FWHM pulse duration at air, and (λ=248nm) carries out the pulse laser fusion, as its full content document and the K.M.Yu that quotes as a reference here, W.Walukiewicz, M.A.Scarpulla as the KrF laser of 38ns; O.D.Dubon, J.Jasinski, Z.Liliental-Weber; J.Wu, J.W.Beeman, M.R.Pillai; M.J.Aziz, J.Appl.Phys.94 is described in 1043 (2003).Through behind the polygon prism homogenizer, the fluence scope at sample place is 0.020 and 0.3J/cm 2Between.The N that behind the PLM part in the sample is being flowed 2In under the temperature between 300 and 700 ℃, carry out the RTA in 10 seconds.
Semiconductor composition of the present invention is useful in photovoltaic application.Caused experiment and theoretical research widely on new material and the battery design in the effort of being done aspect the improvement solar battery efficiency.Up to the present; Use has reached 37% highest energy conversion efficiency based on the multijunction solar cell of standard semiconductor materials; Referring to P.K.Chiang etc., the 183rd page of Proc.25thIEEE Photovoltaic Specialists Conference (IEEE New York, 1996); S.R.Kurtz etc., Proc.26th IEEE Photovoltaic Specialists Conf., (IEEE; New York, 1997) the 875th page and R.R.King etc., Proc.29th IEEE Photovoltaic Specialists Conf.; New Orleans; 2002 (IEEE New York, 2002) 852-5 page or leaf, the full content of its all three documents is incorporated this paper into as a reference.
Utilization is in the many band gap in the solar energy spectral limit, Zn 1-yMn yO xTe 1-xA kind of material that is used for solar cell of excellence is provided.Shown in Figure 1 be by 0.04 to 0.3J/cm 2Be injected with 3.3%O behind the PLM under the laser energy fluence that increases +Zn 0.88Mn 0.12A series of PR spectrums of Te sample.By usefulness>=0.08J/cm 2Sample behind the fluence PLM can clearly be observed obviously and the basic band-gap transition (E of matrix M=2.32eV) different two～1.8 with the optical transition of 2.6eV.Identical is not injecting and Ne +PLM on the ZnMnTe sample that injects handles and does not show this transition, and this shows that they are not caused by implant damage.These presentation of results are at O +Inject and energy fluence>=0.08J/cm 2PLM after, form Zn 0.88Mn 0.12O xTe 1-xLayer.Two optical transitions can owing to from valence band to two because the formed sub-band E that leads of hybridization of the ZnMnTe conduction band states of fixing O attitude and extension +(～2.6eV) and E -The transition of (～1.8eV).E -And E +The elongation property of the strong signal indicating at place these electronic states and actual oscillator strength for transition.Zn 0.88Mn 0.12O xTe 1-xThe band structure and the density of states under alloy (x the is about 0.01) situation are as shown in Figure 4.Extended state E -O derive arrowband and top sub-band E +Between approximately separate 0.7eV.In this band structure, three types of optical transitions are possible: (1) is from the valence band to E +Sub-band, E V+=E +(k=0)-E V(k=0)=and 2.56eV, (2) are from the valence band to E -Sub-band, E V-=E -(k=0)-E V(k=0)=1.83eV and (3) are from E -To E +, E +-=E +(k=0)-E -(k=0)=0.73eV.These three absorption edges cover most of solar spectrum, thereby these alloys are excellent candidate materials for the multiband semiconductor that expectation is used for the high efficiency photovoltaic device.
Fig. 2 is 3.3%O +The Zn that injects 0.88Mn 0.12The Te sample is 0.15J/cm in fluence 2Then a series of PR spectrums behind the RTA that carried out for 10 seconds under the temperature between 300 and 700 ℃ of PLM.Can observe E being higher than under 350 ℃ the RTA temperature -And E +The decline of power conversion.This explanation, Zn 0.88Mn 0.12O xTe 1-xAlloy is being heat-staple under～350 ℃ temperature.Under 700 ℃ RTA temperature, only observe original E MTransition.This can think that the O atom diffusion that is in the Te position has exceeded the position of Te, possibly form the O bubble.It should be noted that also the BAC model prediction works as E -Transition is during near fixing O energy level, such as at sample under the situation behind the RTA under the temperature between 400 and 555 ℃, the immobilization more that becomes of the minimizing characteristic of minimum sub-band.This can be used for the expansion of viewed transition in the key diagram 2.
Fig. 3 has drawn the Zn of different x 0.88Mn 0.12O xTe 1-xThe E of alloy -And E +Energy position.The data of picking up from that O (1.65,2.2 and 4.4%) with the difference amount injects and carrying out the sample of PLM with the different-energy fluence also are plotted in Fig. 3.Here we are noted that, along with being higher than fusion threshold value (～0.08J/cm 2) the increase of energy fluence, x reduces; This possibly be because longer fusion duration and/or the dilution that darker fusion penetration causes.The energy position of two transition that the BAC model is predicted is drawn with solid line.Here, because the value of x is from E -Transition is calculated, so E -Do not provide error line.If E +The live width of transition is wide, and for the sample with different O molar fractions, they can be reasonably well consistent with calculated value.
Annealing in process can be carried out through heating or pulse laser fusion (PLM) by thermal annealing (TA).Certainly, term PLA (pulsed laser anneal) and PLM (pulse laser fusion) are used for describing same annealing phenomenon process in semiconductor.Thermal annealing carries out under the temperature that is lower than the wafer semiconductor fusing point.Typical temperature is between 500 and 1200 ℃, and the duration is in second.Pulsed laser anneal is according to people's such as Yu Applied Physics Letters Vol.80, and No.21,3958-3960 (2000) carry out, and its full content is incorporated this paper into as a reference.
For the efficient of semiconductor composition of the present invention in solar cell application is described, calculated the solar cell energy conversion efficiency of material with electronics band structure shown in Figure 4.Even for the band gap configuration of this non-the best, our calculating energy conversion efficiency also is 45%, it is higher than any ideal efficiency based on the solar cell of unijunction in single gap semiconductor, and can compare with the efficient of three junction batteries.
The rectification behavior that the formation of p-n junction is measured through volt-ampere (I-V) as shown in Figure 5 is explained.The photovoltaic effect that also has this structure shown in Figure 5, it has clearly illustrated that the strong absorption at lower～1.7eV band gap place.
The present invention's imagination is passed through Zn 0.88Mn 0.12O xTe 1-xIn x be increased to～0.05, will be with E +And E -Between the interval be increased to 1eV, thereby obtain 56% energy conversion efficiency.What calculate is with Zn by 3- 0.88Mn 0.12O xTe 1-xThe energy conversion efficiency of the solar cell that alloy is made and the relation curve of O content are as shown in Figure 6.
Be noted that in following examples, the time interval that is used to heat as far as possible weak point be preferred.Usually exist an inverse relation between the time of heating and the employed temperature.For specific II-VI family semiconductor, a those of ordinary skill in the art can optimize suitable parameter at an easy rate.
Embodiment
Utilize light modulation reflectivity (PR) to measure under the room temperature according to the composition of the present invention's preparation and the band gap of film.That to send from 300 watts of tungsten halogen lamps and focused on sample by the radiation that the 0.5m monochromator disperses and become probe beam.A branch of interrupted HeCd laser beam (λ=442 or 325nm) provides light modulation.Use is surveyed the PP signal to the sensitive synchronous amplification system of phase change by the Si photodiode.Through the PR spectrum is fitted to the value that Aspnes three order derivative functional forms are measured band gap and live width, referring to D.E.Aspnes, Surf.Sci.37,418 (1973), its full content is incorporated this paper into as a reference.
Embodiment 1: (II family) (x)(A) (1-x)(S or Se) (1-y-z)(Te) (y)(O) z, 0＜x≤1,0＜z＜0.04 and 0＜y＜0.2 wherein.Material can be by following method preparation.With matrix ZnSe 1-yTe y(0＜y＜0.2) is injected with 1～4% O.Adopt the short pulse fusion top layer of laser.Top layer, four belts can mix and form p/n with the p-mold base and tie with the n-type.
Embodiment 2: use described semi-conducting material to prepare solar cell here.With p-mold base Zn 1-yMn yTe (or similar material) injects with the O of 1～4 atom % and the Cl of 0～1 atom %.Use the implanted layer at short laser pulse fusion top then.Have 10 17～10 19Cm -3The regeneration n-type layer of electron concentration and p-mold base form the p/n knot.The back side at matrix forms metallic ohmic contact.Use transparent conductor such as ZnO or InSnO alloy to form the front contact of n-type layer.
Embodiment 3: (II family) (1-y)(A) yO x(VI family) (1-x)Preparation, 0≤y＜1,0＜x＜0.1 wherein, and " A " comprises magnesium.The O of use 90 and 30keV +Carry out multipotency and be injected into Zn 1-yMn yTo form the thick layer of～0.2 μ m, O concentration is constant relatively with respect to the 0.0165-0.044O molar fraction in Te (y=0 and the 0.12) monocrystalline.In air, use the FWHM pulse duration to be～the KrF laser of 38ns (λ=248nm) to O +The sample that injects carries out the pulse laser fusion, and is said as following document: K.M.Yu, W.Walukiewicz, M.A.Scarpulla; O.D.Dubon, J.Jasinski, Z.Liliental-Weber; J.Wu, J.W.Beeman, M.R.Pillai and M.J.Aziz; J.Appl.Phys.94,1043 (2003), its full content is incorporated this paper into as a reference.Through behind the polygon prism homogenizer, the fluence scope on the sample is 0.020 and 0.3J/cm 2Between.The N that behind the PLM part in the sample is being flowed 2In under the temperature between 300 and 700 ℃, carry out the RTA in 10 seconds.
Embodiment 4:GaN xAs 1-x-yP yPreparation, 0.3≤y＜0.5,0＜x＜0.05 wherein.To with respect to the N molar fraction of 0＜x＜0.05, be injected into GaAs by constant relatively N concentration N multipotency 1-yP yIn (0.3＜y＜0.5) monocrystalline to form thin layer.Use the photon fluence that changes to N +The sample that injects carries out the pulse laser fusion.Also can use suitable molecular beam epitaxy and the organometallic chemical vapor thin film epitaxial growth technology in being deposited on that comprises to make the GaN of 0.3≤y＜0.5 wherein and 0＜x＜0.05 xAs 1-x-yP yGrowth.Fig. 7 has shown GaN xAs 1-x-yP yIn with respect to conduction band energy minimum E ΓAnd E XThe nitrogen energy E NThe position of energy level.Work as E NBe in E ΓBelow and E ΓStill be lower than E XDuring minimum, the band of deriving of the nitrogen in the middle of can be well forming.When as shown in Figure 7 this occurs in 0.4＜y＜0.6.
Fig. 8 is GaN xAs 1-x-0.6P 0.4In above E +E with the centre -The relation curve of the energy of conduction band and N content x.Use band anti-cross Model Calculation curve.Curve E + -E -The minimum absorption edge energy that representative can be regulated with the N content of maximum solar battery efficiency.
Embodiment 5:Ga 1-yIn yN xP 1-xPreparation, 0.4≤y＜0.6 and 0＜x＜0.05 wherein.To with respect to the N molar fraction of 0＜x＜0.05, be injected into Ga by constant relatively N concentration N multipotency 1-yIn yIn P (0.4≤y≤0.6) monocrystalline to form thin layer.Use the photon fluence that changes to N +The sample that injects carries out the pulse laser fusion.Also can use suitable molecular beam epitaxy and the organometallic chemical vapor thin film epitaxial growth technology in being deposited on that comprises to make the Ga of 0.3≤y＜0.5 wherein and 0＜x＜0.05 1-yIn yN xP 1-xGrowth.
When not wanting, it is believed that band anti-cross (BAC) model of studying recently can be explained the distinguished and beyond thought characteristic of HMA semiconductor described in the present invention, referring to W.Shan by any concrete theory or principle constraint; W.Walukiewicz, J.W.Ager III, E.E.Haller; J.F.Geisz, D.J.Friedman, J.M.Olson and S.R.Kurtz; Phys.Rev.Lett.82,1221 (1999), its content is incorporated this paper into as a reference.According to this model, the electronic structure of HMAs is determined by the interaction between the extended state of stationary state relevant with N or O atom and nucleus semiconductor substrate.Conduction band splits into two sub-bands that have obvious non-parabola shape dispersion relation as a result.
Conclusion
Although we just describe foregoing invention in detail for the clear purpose of understanding; But those skilled in the art still is to be appreciated that; Under the prerequisite that does not break away from scope of invention and spirit, can accomplish various modifications and change to described preferred embodiment.Therefore, described embodiment should be considered to be illustrative and not be restrictive, and the present invention should not be only limited to given details here, and should be limited appended claims and their whole full scope of equivalents.

Claims (10)

1. semiconductor composition, it comprises:
Comprise GaN xAs 1-x-yP yAlloy, wherein
0.3≤y＜0.5 and 0＜x＜0.05.
2. the semiconductor composition of claim 1, wherein
0.01≤x≤0.04。
3. the semiconductor composition of claim 2, wherein
0.02≤x≤0.03。
4. semiconductor composition, it comprises:
Comprise Ga 1-yIn yN xP 1-xAlloy, wherein
0.4≤y＜0.6，0＜x＜0.05。
5. the semiconductor composition of claim 4, wherein 0.01≤x≤0.04.
6. the semiconductor composition of claim 5, wherein
0.02≤x≤0.03。
7. photovoltaic device, it comprises a kind of semiconductor composition, said composition comprises:
Ternary or quaternary alloy,
Said alloy comprises II family element, VI family element, oxygen and optional the third element " A ", wherein
Said alloy has (II family) (1-y)(A) yO x(VI family) (1-x)Molar fraction form, and 0≤y＜1,0＜x＜1, " A " comprises magnesium.
8. photovoltaic device, it comprises a kind of semiconductor composition, said composition comprises:
Ternary or quaternary alloy,
Said alloy comprises II family element, VI family element, oxygen and optional the third element " A ", wherein
Said alloy has (II family) (1-y)(A) yO x(VI family) (1-x)Molar fraction form, and
0≤y＜1,0＜x＜0.05, " A " comprises manganese or magnesium,
And wherein II family element does not comprise Cd.
9. photovoltaic device, it comprises a kind of semiconductor composition, said composition comprises:
I I family element, optional another kind II family's element " A "; Also comprise S or Se, and comprise oxygen and tellurium, wherein
Said composition has (II family) (x)(A) (1-x)(S or Se) (1-y-z)(Te) (y)(O) zMolar fraction form, and
0＜x≤1，0＜z＜0.04，0＜y＜0.2。
10. photovoltaic device, it comprises the composition of claim 4.
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