CN1165084C - Semiconductor and perovskite structure oxide p-n junction - Google Patents
Semiconductor and perovskite structure oxide p-n junction Download PDFInfo
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- CN1165084C CN1165084C CNB011044594A CN01104459A CN1165084C CN 1165084 C CN1165084 C CN 1165084C CN B011044594 A CNB011044594 A CN B011044594A CN 01104459 A CN01104459 A CN 01104459A CN 1165084 C CN1165084 C CN 1165084C
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Abstract
The present invention relates to a series of novel p-n junctions, which relates to the field of electronics. The present invention is that n-type or p-type perovskite structural oxide (selective doped barium titanate, or strontium titanate or lanthanum manganate) and n-type or p-type semiconductor materials (selective doped silicon or germanium or gallium arsenide) carry out stacked growth to prepare semiconductors and perovskite structural oxide in a p-n junction structure, a p-p junction structure, an n-n junction structure, a p-n-p junction structure, an n-p-n junction structure, etc. The present invention has simple manufacture technology and high stability, and can be widely used for electronic devices and detectors.
Description
The present invention relates to person in electronics, particularly relate to a series of novel p-n junctions.
The discovery of germanium silicon p-n junction makes Human's production, work and life that revolutionary great variety all take place.Perovskite structure oxide is contained a series of critical natures, as characteristic and effects such as dielectric, ferroelectric, photoelectricity, piezoelectricity, thermoelectricity, superconduction, giant magnetoresistance and nonlinear opticses.Though the structure of perofskite type oxide is more complex than germanium silicon, physical property is different, and many perofskite type oxides chemically with on the structure have good compatibility.
No matter in recent years, along with the discovery of phenomenons such as high-temperature superconductor and giant magnetoresistance, worldwide started the research boom of perovskite oxide material, be the exploration and the research of new material, and still relevant theoretical research has all obtained very big progress.Especially the research of high-temperature superconducting thin film and giant magnetoresistive thin film has entered application, development phase.The new material relevant with perovskite structure oxide and the exploration of new unit have become the focus of research and development.We not only develop the SrTiO of n type and p type
3, BaTiO
3, LaMnO
3In material (document 1: Chinese patent, number of patent application: 99108056.4; Document 2: Chinese patent, number of patent application: 99108057.2; Document 3: Chinese patent, number of patent application: 99123795.1; Document 4: Chinese patent, number of patent application: 99123796.x).And prepare the transistor (document 5: Chinese patent, number of patent application: 00100366.6 of strontium titanates, barium titanate and composite perovskite structure oxide membrane; Document 6: Chinese patent, number of patent application: 00100367.4; Document 7: Chinese patent, number of patent application: 00100368.2).
Obviously, p type and the similar of n type different conduction-types or inhomogeneity perovskite structure oxide material be grown in form p-n junction together, because the cross-couplings of performances such as dielectric that the perovskite structure oxide material had, ferroelectric, photoelectricity, thermoelectricity, superconduction, giant magnetoresistance is bound to occur some novel phenomenons, effect and characteristic.If with semiconductors such as perovskite structure oxide and silicon, germanium, the GaAs preparation p-n junction that combines, no matter be structure, characteristic or technology, integrated and use all more meaningful.
The purpose of this invention is to provide a series of different qualities that have, widely used semiconductor and composite perovskite structure oxide membrane p-n junction.Wherein semiconductor is silicon (Si) or germanium (Ge) or GaAs (GaAs); Perovskite structure oxide is the strontium titanates (SrTiO that mixes
3) or barium titanate (BaTiO
3) or lanthanum manganate (LaMnO
3).P-n junction provided by the invention comprises polycrystalline, monocrystalline, amorphous, or polycrystalline, monocrystalline and amorphous replace the many kinds of structures of compound p-n, p-p, n-n, p-n-p, n-p-n of mixing, making comprises multiple devices such as diode, triode, many base stages triode and multi-emitter triode, can be widely used in all kinds of electronics circuits and some detection systems.
The object of the present invention is achieved like this:
To have the SrTiO of dielectric property
3, BaTiO with ferroelectric, dielectric and optical nonlinearity characteristic
3Or LaMnO with giant magnetoresistance characteristic
3Deng perovskite structural material is the basis, adopts doping method, prepares the p type with different conduction-types or the above-mentioned three class thin-film materials of n type.One of above-mentioned three class thin-film materials of same nature or p type of different nature or n type are carried out lamination with semi-conducting material (germanium of doping or silicon or GaAs), form p-n junction, p-p knot, n-n junction, p-n-p knot, n-p-n knot or multijunction structure, promptly prepare semiconductor and composite perovskite structure oxide membrane p-n junction.
Adopt part displacement doping method, the perovskite structure oxide film of preparation p type or n type.Specific practice is: (1) preparation n type strontium titanates SrA
xTi
1-xO
3Or Sr
1-xLa
xTiO
3, wherein A is Nb or Sb or Ta; Preparation p type strontium titanates SrB
xTi
1-xO
3, wherein B is In or Ga or Mn.(2) preparation n type barium titanate BaC
xTi
1-xO
3Or Ba
1-xLa
xTiO
3, wherein C is Nb or Sb or Ta; Preparation p type barium titanate BaD
xTi
1-xO
3, wherein D is In or Ga or Mn.(3) preparation n type lanthanum manganate La
1-xE
xMnO
3, wherein E is Te or Nb or Sb or Ta; Preparation p type lanthanum manganate La
1-xF
xMnO
3, wherein F is Sr or Ca or Ba or Pb or Sn.The span of all x is 0.005-0.5.
With silicon and perovskite structure oxide p-n junction is example, illustrate how the present invention realizes: use laser molecular beam epitaxy, pulsed laser deposition, magnetron sputtering, electron beam evaporation, molecular beam epitaxy, film-forming method such as chemical deposition or vapor phase epitaxy, one deck n type perovskite structure oxide (strontium titanates of doping or barium titanate or lanthanum manganate) is grown on the p type silicon substrate, or one deck p type perovskite structure oxide (strontium titanates of doping or barium titanate or lanthanum manganate) is grown on the n type silicon substrate, then at p-n junction of formation at the interface of perovskite structure oxide and silicon.
One deck n type perovskite structure oxide (strontium titanates of doping or barium titanate or lanthanum manganate) is grown on the n type silicon substrate different with its carrier concentration, then on the interface of perovskite structure oxide and silicon, forms a n-n junction.
One deck p type perovskite structure oxide (strontium titanates of doping or barium titanate or lanthanum manganate) is grown on the p type silicon substrate different with its carrier concentration, then on the interface of perovskite structure oxide and silicon, forms a p-p knot.
Equally, also the silicon growth of n type or p type can be formed p-n junction, n-n junction or p-p knot on n type or p type perovskite structure oxide (strontium titanates of doping or barium titanate or lanthanum manganate) substrate or film.
The perovskite structure oxide (strontium titanates of doping or barium titanate or lanthanum manganate) of n type or p type is carried out the growth of three layer laminate with silicon by the structure of npn or pnp, can form n-p-n knot or p-n-p knot, can prepare n-p-n triode or p-n-p triode with this.For silicon and perovskite structure oxide (ABO
3) n-p-n knot and p-n-p tie, have silicon/(ABO
3)/(ABO
3), silicon/silicon/(ABO
3), silicon/(ABO
3)/silicon and (ABO
3)/silicon/(ABO
3) wait four kinds of structures.If in same p-n-p or n-p-n structure, two-layer ABO is arranged
3, this two-layer ABO
3Can be same a kind of doping of commaterial, also can be that the difference of commaterial is mixed, and can also be that the difference of different materials is mixed.
If strontium titanates and barium-titanate material anoxic, its oxygen room also can make strontium titanates and barium titanate have n type conductive characteristic, therefore when preparation strontium titanates (or barium titanate) and silicon p-n junction, also can not select the strontium titanates (or barium titanate) of doping for use, and the strontium titanates (or barium titanate) of under low oxygen pressure, growing, making it form the oxygen room becomes n type strontium titanates (or barium titanate).
The p-n junction of perovskite structure oxide and silicon and germanium silicon p-n junction are similar, can design as required, and both can be planar growth, also can be selective area growth forms, can also be corrosion or etching form.The perovskite structure oxide and the silicon thin film of preparation p-n junction lamination or selective area growth can be polycrystalline, amorphous, and monocrystalline also can be the alternatively mixing and the growth of polycrystalline, amorphous and monocrystalline.Drawing and encapsulating of perovskite structure oxide and silicon p-n junction can be used the existing device and the technology of silicon germanium bipolar transistor fully, adopts photoetching, corrosion or etching, electrode evaporation.As needs and silicon transistor first deposit one deck SiO before the etching lead-in wire
2The same, at the upper surface growth dielectric isolation layer of perovskite structure oxide and silicon p-n junction or p-p knot or n-n junction or p-n-p knot or n-p-n knot film.Dielectric isolation layer can be SiO
2Or SrTiO
3Or ZrO
2Or BaTiO
3Or LaAlO
3Or Al
2O
3, and then etch and draw electrode hole, evaporated metal layer, photoetching, etching lead-in wire, encapsulation also can be adopted the existing shell of germanium silicon circuit.
Same as above, replace silicon with germanium or GaAs, just can prepare the different structures such as p-n junction, p-p knot, n-n junction, p-n-p knot, n-p-n knot of germanium or GaAs and perovskite structure oxide.
Because performances such as the dielectric that has of perovskite structure oxide material, ferroelectric, photoelectricity, thermoelectricity, superconduction, giant magnetoresistances, therefore semiconductor provided by the invention and perovskite structure oxide p-n junction will become a kind of electronic device with characteristics and extensive use.
The present invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is BaMn
0.2Ti
0.8O
3(p)/Si (n) structure p-n junction volt-ampere of characteristic diode curve,
Fig. 2 is SrIn
0.1Ti
0.9O
3(p)/Si (n) structure p-n junction volt-ampere of characteristic diode curve,
Fig. 3 is BaNb
0.3Ti
0.7O
3(n)/Si (p) structure p-n junction volt-ampere of characteristic diode curve.
Fig. 4 is La
0.7Sr
0.3MrO
3(p)/Si (n) structure p-n junction volt-ampere of characteristic diode curve.
Using laser molecular beam epitaxy, is 2～6 Ω .cm in resistivity, the thick amorphous BaMn of growth 250nm on 2 inches single-sided polishing n type single crystalline Si substrates
0.2Ti
0.8O
3Film cuts into the tube core of 1mm * 1mm with the Si substrate of the film of having grown, and does electrode in the upper and lower surface of each tube core with the indium 0.1mm copper wire of burn-oning respectively, prepares silicon and barium titanate p-n junction diode.
Fig. 1 is the volt-ampere characteristic that above-mentioned diode records.
Press embodiment 1 and make, use Sr
0.6La
0.4TiO
3Replace BaMn
0.2Ti
0.8O
3Epitaxial growth prepares silicon and strontium titanates p-n junction crystal diode on n type Si substrate.
Press embodiment 1 and make, use the magnetron sputtering film-forming method, preparation silicon and barium titanate p-n junction diode.
Press embodiment 1 and make, use molecular beam epitaxial method, the thick SrIn of epitaxial growth 200nm on n type Si substrate
0.1Ti
0.9O
3Film, preparation silicon and strontium titanates p-n crystal diode.
Fig. 2 is the volt-ampere characteristic that above-mentioned diode records.
Embodiment 5
Using laser molecular beam epitaxy, is 0.1～0.5 Ω cm in resistivity, the thick SrNb of growth 300nm on the p type single crystalline Si substrate of 3 inches single-sided polishings
0.3Ti
0.7O
3Film, preparation silicon and strontium titanates p-n diode.
Embodiment 6
Using laser molecular beam epitaxy, is the thick BaNb of growth 200nm on the n type single crystalline Si substrate of 2 inches single-sided polishings of 2～6 Ω cm in resistivity
0.3Ti
0.7O
3Preparation silicon and barium titanate n-n diode.
Fig. 3 is the volt-ampere characteristic that above-mentioned diode records.
Embodiment 7
Press embodiment 6 and make, use SrSb
0.3Ti
0.7O
3Replace BaNb
0.3Ti
0.7O
3, preparation silicon and strontium titanates n-n diode.
Embodiment 8
Press embodiment 6 and make, use La
0.7Sr
0.3MnO
3Replace BaNb
0.3Ti
0.7O
3, preparation silicon and lanthanium manganate p-n diode.
Embodiment 9
Use magnetron sputtering method, SrTa
0.05Ti
0.95O
3Being grown in resistivity is on the p type Si substrate of 0.03～0.08 Ω cm, preparation silicon and strontium titanates p-n diode.
Embodiment 10
Use the pulsed laser deposition method, BaTa
0.5Ti
0.5O
3Being grown in resistivity is on the p type monocrystalline silicon of 200～250 Ω cm, preparation silicon and barium titanate p-n junction diode.
Embodiment 11
Use chemical deposition, Ba
0.7La
0.3TiO
3Being grown in resistivity is on the p type single crystalline Si of 1～5 Ω cm, preparation silicon and barium titanate p-n junction diode.
Embodiment 12
Pressing embodiment 1 and make, is 2 inches n type germanium replacement silicon of 2～6 Ω cm with resistivity, preparation germanium and barium titanate p-n junction diode.
Embodiment 13
Use laser molecular beam epitaxy, La
0.7Sr
0.3MnO
3Being grown in resistivity is on the p type monocrystalline silicon of 200～250 Ω cm, preparation silicon and lanthanum manganate p-p junction diode.
Fig. 4 is the volt-ampere characteristic that above-mentioned diode records.
Embodiment 14
Use the pulsed laser deposition method, SrGa
0.25Ti
0.75O
3Being grown in resistivity is on the n type monocrystalline germanium of 0.2～0.5 Ω cm, preparation germanium and strontium titanates p-n junction diode.
Embodiment 15
Use laser molecular beam epitaxy, SrMn
0.5Ti
0.5O
3Being grown in resistivity is on the p type monocrystalline GaAs of 200～250 Ω cm, preparation GaAs and strontium titanates p-p junction diode.
Embodiment 16
Pressing embodiment 1 and make, is 2 inches n p type gallium arensideps replacement silicon of 2～6 Ω cm with resistivity, preparation GaAs and barium titanate p-n junction diode.
Embodiment 17
Use the pulsed laser deposition method, La
0.65Ba
0.35MnO
3Being grown in resistivity is on the n type monocrystalline germanium of 200～250 Ω cm, preparation germanium and lanthanum manganese oxygen p-n junction diode.
Embodiment 18
Use laser molecular beam epitaxy, La
0.85Pb
0.15MnO
3Being grown in resistivity is on the p type monocrystalline GaAs of 20～25 Ω cm, preparation GaAs and lanthanum manganate p-p junction diode.
Embodiment 19
Use laser molecular beam epitaxy, selecting resistivity for use is 0.2～0.5 Ω cm, and 4 inches n type single crystalline Si are done the emitter e of substrate and triode, the thick BaIn of growth 500nm on n type Si
0.3Ti
0.7O
3Be base stage b, again at BaIn
0.3Ti
0.7O
3Last growth BaNb
0.1Ti
0.9O
3Be collector electrode c.Etch the semicircular ring base stage b electrode hole of circular collector electrode c of Φ 30 μ m and Φ 40～50 μ m respectively with the method for photoetching and particle beams etching, at the good film surface of the etching SiO of deposit 500nm again
2Do the insulation separator, at separator SiO
2Last photoetching and etch contact conductor, the pressure welding lead-in wire, the tube sealing shell is prepared into silicon and barium titanate n-p-n triode.
Embodiment 20
Press embodiment 19 preparations, around collector electrode c, prepare 3 base stage b, be prepared into many base silicon and barium titanate n-p-n triode.
Embodiment 21
Press embodiment 19 preparations, use SrGa
0.15Ti
0.85O
3Replace BaIn
0.3Ti
0.7O
3Be base stage b, use SrNb
0.05Ti
0.95O
3Replace BaNb
0.1Ti
0.9O
3Be collector electrode c.Preparation silicon and strontium titanates n-p-n triode.
Embodiment 22
Press embodiment 19 preparations, replace n type silicon, use La with p silicon type
0.7Te
0.3MnO
3Replace BaIn
0.3Ti
0.7O
3Be base stage b, use La
0.1Sn
0.9Replace BaNb
0.1Ti
0.9O
3Be collector electrode c.Preparation silicon and lanthanium manganate p-n-p triode.
Embodiment 23
Press embodiment 21 preparations, replace silicon with germanium, preparation germanium and strontium titanates n-p-n triode.
Embodiment 24
Press embodiment 21 preparations, replace silicon with GaAs, preparation GaAs and strontium titanates n-p-n triode.
Embodiment 25
Press embodiment 19 preparations, use SrNb
0.05Ti
0.95O
3Replace BaNb
0.1Ti
0.9O
3Be collector electrode c.Preparation silicon/barium titanate/strontium titanate n-p-n triode.
Embodiment 26
Press embodiment 19 preparations, use La
0.7Te
0.3MnO
3Replace BaIn
0.3Ti
0.7O
3Be base stage b, preparation silicon/lanthanum manganate/barium titanate n-p-n triode.
Embodiment 27
Press embodiment 19 preparations, at the BaIn that is base stage b
0.3Ti
0.7O
3Growth 400nm carrier concentration is 10 on the film
16N type Si replace BaNb
0.1Ti
0.9O
3Be collector electrode c, be prepared into silicon and barium titanate n-p-n triode.
Embodiment 28
Use molecular beam epitaxial method, the n type silicon of selecting for use resistivity to be about 200 Ω cm is substrate and collector electrode c, and the p type silicon that extension 300nm is thick on n type silicon substrate is base stage b, the thicker SrNb of extension 400nm on the silica-based utmost point b of p type
0.4Ti
0.6O3 does emitter e.Preparation silicon and strontium titanates n-p-n transistor.
Embodiment 29
Press embodiment 28 preparations, replace silicon to be collector electrode c and base stage b with germanium, preparation germanium and strontium titanates n-p-n transistor.
Embodiment 30
Use the laser molecular beam epitaxy method, the n type silicon of selecting for use resistivity to be about 200 Ω cm is substrate and collector electrode c, the thick La of extension 300nm on n type silicon substrate
0.8Sr
0.2MnO
3Be base stage b, the thicker SrNb of extension 400nm on base stage b
0.4Ti
0.6O3 does emitter e.Preparation silicon/lanthanum manganate/strontium titanates n-p-n transistor.
Embodiment 31
Use molecular beam epitaxy, selecting resistivity for use is that 4 inches p type Si of 0.01～0.05 Ω cm are substrate, and does emitter e, the thick BaNb of extension 1 μ m on p type Si
0.1Ti
0.9O
3Be base stage b, again at BaNb
0.1Ti
0.9O
3Film on the SrMn of extension 350m
0.05Ti
0.95O
3Be collector electrode c, prepare collector electrode 20 μ m * 20 μ m, the silicon of base stage 50 μ m * 50 μ m/barium titanate/strontium titanate p-n-p transistor with photoetching and etching.
Embodiment 32
Press embodiment 31 and make, replace silicon to do substrate and emitter e, preparation GaAs/barium titanate/strontium titanate p-n-p triode with the p p type gallium arensidep.
Embodiment 33
Use the laser molecular beam epitaxy method, at 40mm * 40mmSrTiO
3The BaNb of extension 800nm at first in the substrate
0.05Ti
0.95O
3Film is collector electrode c, at BaNb
0.05Ti
0.95O
3Extension 350m carrier concentration about 10 on the film
17P type Si be base stage b, the SrNb of extension 400nm on p type Si again
0.4Ti
0.6O
3Do emitter e.SiO with 500nm
2Do the insulation separator, prepare electrode and lead-in wire, preparation n-p-n type barium titanate/silicon/strontium titanate crystals triode with photoetching and particle beams etching.
Embodiment 34
Press embodiment 33 and make, use La
0.8Sr
0.2MrO
3Replace p type silicon to be base stage b, preparation barium titanate/lanthanum manganate/strontium titanates n-p-n transistor.
Embodiment 35
Press embodiment 33 and make, with 2 inches ZrO
2Do substrate and replace SrTiO
3, with carrier concentration about 10
17The p p type gallium arensidep be base stage b, the preparation barium titanate/GaAs/strontium titanates n-p-n transistor.
Claims (2)
1. semiconductor and strontium titanates p-n junction is characterized in that: silicon or germanium or the GaAs of the semiconductor of n type and p type for mixing; N type strontium titanates SrA
xTi
1-xO
3Or Sr
1-xLa
xTiO
3, wherein A is Nb or Sb or Ta; P type strontium titanates SrB
xTi
1-xO
3, wherein B is In or Ga or Mn; X=0.005～0.5; This p type or n type strontium titanates and this n type or p N-type semiconductor N are carried out layer-by-layer growth, and the preparation semiconductor is tied with strontium titanates p-n junction, p-p knot, n-n junction, n-p-n knot, p-n-p.
2. by described semiconductor of claim 1 and strontium titanates p-n junction, it is characterized in that: selected strontium titanates and semi-conducting material are polycrystalline, amorphous, the mixed material of monocrystalline or polycrystalline, amorphous and monocrystalline.
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|---|---|---|---|
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| CN1165084C true CN1165084C (en) | 2004-09-01 |
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| CN100573060C (en) * | 2005-05-24 | 2009-12-23 | 中国科学院物理研究所 | A kind of quick response broadband optical detector |
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| CN101651151B (en) * | 2008-08-12 | 2012-04-18 | 中国科学院物理研究所 | Heterostructure field effect transistor with functional characteristics |
| CN101826549B (en) * | 2009-03-05 | 2012-06-13 | 中国科学院物理研究所 | Semiconductor heterostructure, preparation method thereof and semiconductor device |
| CN101964364B (en) * | 2009-07-24 | 2012-05-23 | 中国科学院物理研究所 | Transistor device and manufacturing method thereof |
| JP2012206890A (en) * | 2011-03-29 | 2012-10-25 | Tdk Corp | Semiconductor ceramic, and multilayer semiconductor ceramic capacitor |
| WO2013171520A1 (en) | 2012-05-18 | 2013-11-21 | Isis Innovation Limited | Optoelectronic device comprising perovskites |
| CN103346255B (en) * | 2013-06-26 | 2014-12-10 | 济南大学 | Heterojunction, ferroelectric tunnel junction and preparation method and application thereof |
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Cited By (1)
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| CN100573060C (en) * | 2005-05-24 | 2009-12-23 | 中国科学院物理研究所 | A kind of quick response broadband optical detector |
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