CN1722390A - Epitaxial growth iron-based alloy thin films and heterojunction materials and preparation method on silicon chip - Google Patents
Epitaxial growth iron-based alloy thin films and heterojunction materials and preparation method on silicon chip Download PDFInfo
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- CN1722390A CN1722390A CN 200410068866 CN200410068866A CN1722390A CN 1722390 A CN1722390 A CN 1722390A CN 200410068866 CN200410068866 CN 200410068866 CN 200410068866 A CN200410068866 A CN 200410068866A CN 1722390 A CN1722390 A CN 1722390A
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Abstract
The present invention relates to epitaxial growth iron-based alloy film and heterojunction material and preparation method on silicon chip, this material is included in the iron-based alloy La of growth one deck p type on the n type silicon chip
1-xA
xMnO
3Film forms the p-n heterojunction material; Wherein A is: Ca, Sr, Ba, Pb or Sn, and the span of all x is 0.05～0.5; Or the iron-based alloy La of one deck n type of on p type silicon chip, growing
1-xB
xMnO
3Film forms the p-n heterojunction material; Wherein B is: Ce, Pr, Te, Nb, Sb or Ta, the span of all x is 0.05～0.5.The preparation method adopts two-step method, with the direct epitaxial growth of the lanthanum manganate material of lanthanum manganate or doping on silicon substrate, or the lanthanum manganate of on silicon chip, growing or iron-based alloy as resilient coating, and then other perovskite oxide film of epitaxial growth, or multilayer film.
Description
Technical field
The present invention relates to a kind of epitaxial growth heterogenous junction film material, particularly a kind of on silicon chip epitaxial growth iron-based alloy film and heterojunction material and preparation method.
Background technology
Lanthanum manganate (the LaMnO that mixes
3) be a kind of functional material with giant magnetoresistance characteristic, as document 1:Ken-ichi Chahara, Toshiyuki Ohno, Masahiro Kafai and Yuzoo Kozono, Appl.Phys.Lett.63,1990 (1993); With document 2:S.Jin, T.H.Tiefel, M.McCormack, R.A.Fastnacht, R.Ramesh, and L.H.Chen, Science 264,423 (1994)) introduced.This material has a wide range of applications at aspects such as magnetic head, magnetic storage, transducer and magnetic control systems, as document 3:M.Rajeswari, A.Goyal, A.K.Raychaudhuri, M.C.Robson, G.C.Xiong, C.Kwon, R.Ramesh, R.L.Greene and T.Venkatesan, Appl.Phys.Lett.69 is described in 851 (1996).As China Patent No.: ZL 98101982.X discloses a kind of material of giant magnetoresistance p-n junction structure.China Patent No.: ZL 01 1 04460.8 discloses a kind of semiconductor and lanthanium manganate p-n junction material.Up to the present, the giant magnetic resistor material of being introduced in the document also not the direct epitaxial growth of iron-based alloy in silicon (Si) substrate.
Summary of the invention
One of purpose of the present invention is: provide a kind of on silicon chip, the iron-based alloy thin-film material that direct epitaxial growth has the giant magnetoresistance characteristic particularly provides a kind of method for preparing this material;
Two of purpose of the present invention be to provide a kind of the direct epitaxial growth of iron-based alloy film on silicon chip, can also directly on silicon chip, prepare the dopant acid lanthanum film, form p-n or the p-p or the n-n heterojunction material of iron-based alloy/silicon, also can be the lanthanum manganate that on silicon chip, prepares and iron-based alloy as resilient coating, the other one deck perovskite oxide film of epitaxial growth thereon or epitaxial growth multilayer film heterojunction material and preparation method again.
The object of the present invention is achieved like this:
Provided by the invention on silicon chip epitaxial growth iron-based alloy thin films and heterojunction materials, comprise following composition:
With n type or p type silicon chip is substrate;
The iron-based alloy La of growth one deck p type on its n type silicon chip substrate
1-xA
xMnO
3Film forms the p-n heterojunction material; Wherein A is: Ca, Sr, Ba, Pb or Sn, and the span of all x is 0.05～0.5;
Or the iron-based alloy La of one deck p type of on p type silicon chip substrate, growing
1-xA
xMnO
3Film forms the p-p heterojunction material; Wherein A is: Ca, Sr, Ba, Pb or Sn, and the span of all x is 0.05～0.5;
Or the iron-based alloy La of one deck n type of on p type silicon chip substrate, growing
1-xB
xMnO
3Thin-film material forms the p-n heterojunction material; Wherein B is: Ce, Pr, Te, Nb, Sb or Ta, the span of all x is 0.05～0.5.
Or the iron-based alloy La of one deck n type of on n type silicon chip substrate, growing
1-xB
xMnO
3Thin-film material forms the n-n heterojunction material; Wherein B is: Ce, Pr, Te, Nb, Sb or Ta, the span of all x is 0.05～0.5.
Also be included in the lanthanum manganate that prepared on the silicon chip substrate and iron-based alloy thin layer as resilient coating, one or more layers other perovskite oxide film in addition of epitaxial growth thereon again is for example the LaMnO that has prepared
3Film is as resilient coating, the thick BaTiO of epitaxial growth 300nm in the Si substrate
3Film.Perhaps prepare BaNb
0.05Ti
0.95O
3/ La
0.7Sr
0.3MnO
3The n-p-n-p-n-p sandwich construction film of/Si, or use BaNb
0.05Ti
0.95O
3The target of high temperature sintering replaces SrNb
0.1Ti
0.9O
3, preparation BaNb
0.05Ti
0.95O
3La
0.7Sr
0.3MnO
3The n-p-n-p-n-p sandwich construction of/Si.
Described perovskite oxide comprises: YBCO, BaTiO
3, LaAlO
3, SrTiO
3And the BaTiO that mixes
3, SrTiO
3
The BaTiO of described doping
3Comprise: n type barium titanate BaA
xTi
1-xO
3Or Ba
1-xLa
xTiO
3Thin-film material, wherein A is Nb or Ta; P type barium titanate BaB
xTi
1-xO
3, wherein B is In, Ga or Mn; The span of all x is 0.005～0.5.
The SrTiO of described doping
3Comprise: n type strontium titanates SrA
xTi
1-xO
3Or Sr
1-xLa
xTiO
3Thin-film material, wherein A is Nb or Ta; P type strontium titanates SrB
xTi
1-xO
3, wherein B is In, Ga or Mn; The span of all x is 0.005～0.5.
Provided by the invention on silicon chip the preparation method of epitaxial growth iron-based alloy thin films and heterojunction materials, be included in laser molecular beam epitaxy or the pulsed laser deposition device and carry out according to the following steps:
1. select the lanthanum manganate or the composite mixed lanthanum manganate target of high temperature sintering for use, the iron-based alloy La of described p type
1-xA
xMnO
3Target, wherein A is: Ca, Sr, Ba, Pb or Sn, the span of all x is 0.05～0.5;
The iron-based alloy La of described n type
1-xB
xMnO
3Target, wherein B is: Ce, Pr, Te, Nb, Sb or Ta, the span of all x is 0.05～0.5;
2. selecting n type or p type silicon chip after (100) alignment surfaces is polished for use is substrate;
3. the selected backing material of step 2 is carried out the silicon chip chemical cleaning of semiconductor standard, silicon chip after cleaning up is directly taken out from the hydrofluoric acid washing lotion, perhaps select the silicon chip of exempting to clean for use, silicon chip in the hydrofluoric acid washing lotion after the rinsing, and in the Sample Room or epitaxial chamber in the epitaxial apparatus of packing at once;
4. after silicon chip is put into epitaxial chamber, epitaxial chamber's vacuum degree is evacuated to is better than 1 * 10
-2Pa carries out epitaxial growth; Described epitaxial growth comprises the first step: because silicon activity very, be easy to form oxide layer at silicon chip surface, therefore at first in the temperature range of room temperature to 400 ℃, at the silicon chip surface of hydrogen bond protection or firm when volatilized at the silicon chip surface hydrogen bond, use pulsed laser deposition, the iron-based alloy of 1～20 primitive unit cell layer of sputter so just can be avoided the silicon chip surface oxidation on silicon chip;
Second step: there is the silicon chip of 1～20 primitive unit cell layer iron-based alloy on the surface that first step sputter is obtained, be heated to 450 ℃～850 ℃, make iron-based alloy form crystallization, with the crystallization situation of reflection high energy electron diffraction (RHEED) observation iron-based alloy material at silicon chip surface; After the RHEED of iron-based alloy diffraction fringe occurs, the iron-based alloy material be described in silicon chip surface formation crystallization, just iron-based alloy extension at silicon chip surface; Just can feed the mobile oxygen of 2 * 10-4Pa～100Pa then to epitaxial chamber, and, carry out continuous epitaxial growth iron-based alloy film with the frequency continuous emission excimer laser pulse of 1～10Hz;
5. after Zhi Bei thickness reaches requirement, stop laser splash, the mobile oxygen when keeping epitaxial growth is reduced to room temperature to sample temperature, takes out sample from epitaxial chamber then, and preparation process is finished.
Also be included in after step 4 finishes, as resilient coating, adopt conventional epitaxy method at the lanthanum manganate that has prepared and iron-based alloy thin layer more thereon, continued growth is one or more layers other perovskite oxide film in addition.Described perovskite oxide comprises: YBCO, BaTiO
3, LaAlO
3, SrTiO
3And the BaTiO that mixes
3, SrTiO
3
The BaTiO of described doping
3Comprise: n type barium titanate BaA
xTi
1-xO
3Or Ba
1-xLa
xTiO
3Thin-film material, wherein A is Nb or Ta; P type barium titanate BaB
xTi
1-xO
3, wherein B is In, Ga or Mn; The span of all x is 0.005～0.5.
The SrTiO of described doping
3Comprise: n type strontium titanates SrA
xTi
1-xO
3Or Sr
1-xLa
xTiO
3Thin-film material, wherein A is Nb or Ta; P type strontium titanates SrB
xTi
1-xO
3, wherein B is In, Ga or Mn; The span of all x is 0.005～0.5.
Described is silicon chip rinsing time in the hydrofluoric acid washing lotion 1 second-5 minute.
The described pressure to the epitaxial chamber aerating oxygen is 2 * 10-4Pa～100Pa, and with the frequency continuous emission excimer laser pulse of 1～10Hz, carries out continuous epitaxial growth iron-based alloy film.
The material of above-mentioned lanthanum manganate/silicon heterostructure provided by the invention itself is exactly the functional material with magnetic characteristic, can also be prepared into lanthanum manganate/silicon heterogenous and multilayer film multiple devices such as diode with magnetic characteristic, triode.Material provided by the invention has a wide range of applications at aspects such as magnetic head, magnetic storage, transducer, magnetic control system and electronics.
The invention has the advantages that:
The iron-based alloy film that the present invention is prepared and the material of lanthanum manganate/silicon heterostructure are the epitaxial growth methods that adopts, obtain having the iron-based alloy film and the lanthanum manganate/silicon heterostructure material of good crystal structure, this material itself is exactly the functional material with good magnetic characteristics, the distillation characteristic of its diode as shown in Figure 4, the multiple devices such as diode, triode that therefore, can have magnetic characteristic with lanthanum manganate/silicon heterogenous and multilayer film preparation.
Equally, also can select the lanthanum manganate target for use, epitaxial growth lanthanum manganate film on silicon chip.
In addition, because the oxide of perovskite structure structurally has good compatibility, therefore also can use method provided by the invention, epitaxially grown lanthanum manganate on silicon chip or iron-based alloy film as resilient coating, are grown as YBCO, BaTiO on lanthanum manganate or iron-based alloy film again
3, LaAlO
3, SrTiO
3And the BaTiO that mixes
3, SrTiO
3Deng at the compatible perovskite oxide film of structure, heterojunction and super crystal lattice material.
Preparation method of the present invention owing to adopt directly takes out the silicon chip after cleaning up from the hydrofluoric acid washing lotion, perhaps select the silicon chip of exempting to clean for use, silicon chip in the hydrofluoric acid washing lotion after the rinsing, and in the Sample Room or epitaxial chamber in the epitaxial apparatus of packing at once; Can form one deck hydrogen bond protective layer at silicon chip surface like this, make silicon chip surface not oxidized, particularly utilize laser splash method extension to be divided into two-step method again, thereon directly epitaxial growth/iron-based alloy material.Under present perovskite structure oxide backing material size situation little and of low quality, epitaxial growth method provided by the invention, not only the simple cost of technology is low, solved the substrate problem of large-size high-quality, especially epitaxially grown iron-based alloy thin-film material and iron-based alloy/silicon heterogenous itself all are the materials with magnetic functional characteristic, therefore have range of application and using value very widely.
Provided by the invention on silicon the method for epitaxial growth lanthanum manganate, not only can directly prepare iron-based alloy material and device with magnetic function, and can be used as other perovskite oxide film of resilient coating epitaxial growth, heterojunction and super crystal lattice material, especially can be coupled perovskite oxide material with functional characteristic and silicon integrated circuit, have great importance and application prospects.
Description of drawings
Fig. 1 is 5 primitive unit cell layer La of growth in n type Si substrate
0.7Sr
0.3MnO
3RHEED diffraction fringe.
Fig. 2 is the thick La of epitaxial growth 400nm in p type Si substrate
0.8Sr
0.2MnO
3The RHEED diffraction fringe of film.
Fig. 3 is the thick La of growth 500nm in n type Si substrate
0.7Sr
0.3MnO
3X ray θ-2 θ diffraction curve.
Fig. 4 is the thick La of growth 500nm in n type Si substrate
0.7Sr
0.3MnO
3Film is from the La of this sample formation
0.7Sr
0.3MnO
3/ Si p-n junction, the I-V curve that measures.
Specific embodiment
The present invention will be further described below in conjunction with accompanying drawing and concrete preparation method:
Carry out the thick La of epitaxial growth 500nm on n. type silicon chip with the conventional laser molecular beam epitaxial device
0.7Sr
0.3MnO
3Film.
This La
0.7Sr
0.3MnO
3Film itself is exactly the magnetic functional material with magnetoresistance characteristics, and by La
0.7Sr
0.3MnO
3The heterojunction that/Si constitutes is exactly a p-n thin films and heterojunction materials with good magnetic functional characteristic.
The La of present embodiment
0.7Sr
0.3MnO
3The concrete preparation process of thin films and heterojunction materials is:
1. select 2 inches single-sided polishing n type single crystalline Si substrates of exempting to clean for use;
2. select the p type La of high temperature sintering for use
0.7Sr
0.3MnO
3Target;
3. after 10 seconds of rinsing in the 1% hydrofluoric acid washing lotion, the epitaxial chamber of directly silicon chip being packed into;
4. the vacuum of epitaxial chamber is evacuated to 2 * 10
-5Pa uses the excimer laser of exporting energy 250mJ, the La of sputter in the Si substrate～5 a primitive unit cell layer (～120 laser pulses)
0.7Sr
0.3MnO
3Film was raised to 600 ℃ with 10 minutes with silicon temperature, with reflective high energy resistance diffractometer (RHFFD) observation La
0.7Sr
0.3MnO
3The crystallization situation of film waits the diffraction fringe of RHEED back (as shown in Figure 1) to occur, and La is described
0.7Sr
0.3MnO
3Film has formed crystallization at silicon chip surface.With the pulse laser frequency of per second 2Hz, begin continuous laser splash epitaxial growth, simultaneously to the logical people 2 * 10 of epitaxial chamber
-2The mobile oxygen of Pa, the thick La of preparation 500nm
0.7Sr
0.3MnO
3Film after the thickness of preparation reaches requirement, stops laser splash, keeps 2 * 10
-2The mobile oxygen of Pa was reduced to room temperature to sample temperature with 20 minutes, took out sample from epitaxial chamber then, and preparation process is finished.
Fig. 1 is above-mentioned～5 a primitive unit cell layer La
0.7Sr
0.3MnO
3The RHEED diffraction fringe of film illustrates at silicon chip surface to have formed La
0.7Sr
0.3MnO
3Epitaxial loayer.
Fig. 3 is the above-mentioned thick La of 500nm that grows in n type Si substrate
0.7Sr
0.3MnO
3X ray θ-2 θ diffraction curve, except La
0.7Sr
0.3MnO
3Outside (001) diffraction maximum of film, do not have other assorted peak, illustrate on the Si substrate, to have obtained the good La of orientation
0.7Sr
0.3MnO
3Epitaxial film.
Fig. 4 is the thick La of growth 500nm in the said n type Si substrate
0.7Sr
0.3MnO
3Film is from the La of this sample formation
0.7Sr
0.3MnO
3/ Si p-n junction, the I-V curve that measures.From the I-V curve as can be seen, its p-n junction has good rectification characteristic, therefore can be equipped with diode with this p-n junction body plan.We use superconducting quantum interference device, have observed the magnetoresistance characteristics of this p-n junction.
The La for preparing 800nm by the method for embodiment 1
0.8Sr
0.2MnO
3Film and La
0.8Sr
0.2MnO
3/ Si p-p ties thin films and heterojunction materials.
Selecting p type silicon chip for use is substrate, selects the La of p type high temperature sintering for use
0.8Sr
0.2MnO
3Target, all the other conditions be with embodiment 1, different condition: during epitaxial growth the logical people 3 * 10 of epitaxial chamber
-1The active oxygen of Pa, the La of preparation 800nm
0.8Sr
0.2MnO
3Film and La
0.8Sr
0.2MnO
3/ Si p-p thin films and heterojunction materials.
Fig. 2 is the thick La of epitaxial growth 400nm in p type Si substrate
0.8Sr
0.2MnO
3The RHEED diffraction fringe of film.Sharp and RHEED diffraction fringe clearly illustrates epitaxially grown La on p type Si substrate
0.8Sr
0.2MnO
3Film not only has good crystallinity, and surfacing.
Press the method for embodiment 1, preparation is a substrate with n type single crystalline Si, the La behind the epitaxial growth 800nm
0.9Ca
0.1MnO
3Film and La
0.9Ca
0.1MnO
3/ Si p-n heterojunction material.
With p type La
0.9Ca
0.1MnO
3Target leads to people 3 * 10 in epitaxial chamber during epitaxial growth
-1The active oxygen of Pa, the La of preparation 800nm
0.9Ca
0.1MnO
3Film and La
0.9Ca
0.1MnO
3/ Si p-n junction.
The La for preparing 300nm by the method for embodiment 1
0.7Pr
0.3MnO
3Film and La
0.7Pr
0.3MnO
3/ Si n-n heterojunction material.
With n type single crystalline Si is substrate, with n type La
0.7Pr
0.3MnO
3Target, the La of preparation 300nm
0.7Pr
0.3MnO
3Film and La
0.7Pr
0.3MnO
3/ Si n-n heterojunction material.
Embodiment 5
Prepare the thick La of 300nm by embodiment 1 method
0.7Sr
0.3MnO
3Film and La
0.7Sr
0.3MnO
3/ Si p-n heterojunction material.
Different is with embodiment 1: select 4 inches p type Si single crystal substrates for use, select La for use
0.7Sr
0.3MnO
3P type target; With semiconductor standard Si chemical cleaning method cleaning silicon chip, the thick La of preparation 300nm
0.7Sr
0.3MnO
3Film and La
0.7Sr
0.3MnO
3/ Si p-n heterojunction material.。
Embodiment 6
Use laser molecular beam epitaxy, select 2 inches single-sided polishing n type single crystalline Si substrates of exempting to clean for use, after 10 seconds of rinsing in the 5% hydrofluoric acid washing lotion, the epitaxial chamber of directly silicon chip being packed into is evacuated to 2 * 10 to the vacuum of epitaxial chamber
-4Pa uses the excimer laser of exporting energy 300mJ, the La of sputter in the Si substrate～10 a primitive unit cell layer (～200 laser pulses)
0.7Sr
0.3MnO
3Film was raised to 700 ℃ with 10 minutes with silicon temperature, observed La with RHEED
0.7Sr
0.3MnO
3The crystallization situation of film waits the diffraction fringe of RHFFD back (as shown in Figure 1) to occur, and the laser frequency with per second 4Hz begins continuous laser splash epitaxial growth, simultaneously to the logical people 2 * 10 of epitaxial chamber
-2The mobile oxygen of Pa, the thick La of first epitaxial growth 50nm
0.7Sr
0.3MnO
3Film, the thick SrNb of epitaxial growth 30nm successively then
0.1Ti
0.9O
3, La that 50nm is thick
0.7Sr
0.3MnO
3, SrNb that 30nm is thick
0.1Ti
0.9O
3With the thick La of 50nm
0.7Sr
0.3MnO
3, when the rete of preparation with after thickness reaches requirement, stop laser splash, sample temperature is reduced to room temperature with 30 minutes, preparation process is finished.Prepare SrNb
0.1Ti
0.9O
3/ La
0.7Sr
0.3MnO
3The n-p-n-p-n-p sandwich construction film of/Si.
Embodiment 7
Press the method for embodiment 6 and make, preparation BaNb
0.05Ti
0.95O
3/ La
0.7Sr
0.3MnO
3The n-p-n-p-n-p sandwich construction film of/Si.
Different is with embodiment 6: use BaNb
0.05Ti
0.95O
3The target of high temperature sintering replaces SrNb
0.1Ti
0.9O
3, preparation BaNb
0.05Ti
0.95O
3/ La
0.7Sr
0.3MnO
3The n-p-n-p-n-p sandwich construction film of/Si.
Embodiment 8
Use laser molecular beam epitaxy, select 2 inches single-sided polishing n type single crystalline Si substrates of exempting to clean for use, after 10 seconds of rinsing in the 1% hydrofluoric acid washing lotion, the epitaxial chamber of directly silicon chip being packed into is evacuated to 5 * 10 to the vacuum of epitaxial chamber
-6Pa was raised to 300 ℃ with 2 minutes with silicon temperature, the LaMnO of sputter in the Si substrate～2 a primitive unit cell layer
3Film was raised to 650 ℃ with 5 minutes with silicon temperature, observed La with RHEED
0.7Sr
0.3MnO
3The crystallization situation of film waits the diffraction fringe of RHFFD back (as shown in Figure 1) to occur, elects target as BaTiO
3Target is selected the laser frequency of per second 3Hz for use, begins continuous laser splash epitaxial growth, simultaneously to the logical people 2 * 10 of epitaxial chamber
-2The mobile oxygen of Pa, the thick BaTiO of preparation 300nm
3Film.LaMnO
3As resilient coating, the thick BaTiO of epitaxial growth 300nm in the Si substrate
3Film.
Embodiment 9
Press the method for embodiment 8 and make, LaMnO
3As resilient coating, the YBCO superconducting thin film that epitaxial growth 300nm is thick in the Si substrate.
Replace BaTiO with YBCO high temperature sintering target
3Target, with embodiment 8 different condition be: select the laser frequency of per second 5Hz for use, to the logical people 2 * 10 of epitaxial chamber
-2The flowing activity oxygen of Pa is LaMnO
3As resilient coating, the YBCO superconducting thin film that epitaxial growth 350nm is thick in the Si substrate.
Embodiment 10
Pressing the method for embodiment 1, is substrate with n type single crystalline Si, with the p type La with high temperature sintering
0.95Ba
0.05MnO
3Target, the La of preparation 300nm
0.95Ba
0.05MnO
3Film and La
0.95Ba
0.05MnO
3/ Si p-n heterojunction material.
Embodiment 11
Pressing the method for embodiment 1, is substrate with n type single crystalline Si, with the p type La with high temperature sintering
0.6Ba
0.4MnO
3Target, the La of preparation 300nm
0.6Ba
0.4MnO
3Film and La
0.6Ba
0.4MnO
3/ Si p-n heterojunction material.
Embodiment 12
Pressing the method for embodiment 1, is substrate with p type single crystalline Si, with the p type La of high temperature sintering
0.33Pr
0.33Ca
0.33MnO
3Target, the thick La of preparation 300nm
0.33Pr
0.33Ca
0.33MnO
3Film and La
0.33Pr
0.33Ca
0.33MnO
3/ Si p-p heterojunction material.
Embodiment 13
Pressing the method for embodiment 1, is substrate with n type single crystalline Si, with the n type La of high temperature sintering
0.6Ce
0.4MnO
3Target, the thick La of preparation 500nm
0.5Ce
0.4MnO
3Film and La
0.6Ce
0.4MnO
3/ Si n-n heterojunction material.
Embodiment 14
With conventional pulsed laser deposition device, prepare 500 thick La
0.7Sr
0.3MnO
3Film and La
0.7Sr
0.3MnO
3/ Si p-n heterojunction material.
Pressing the process conditions of embodiment 1, is substrate with n type single crystalline Si, with the p type La of high temperature sintering
0.7Sr
0.3MnO
3Target; Different is with embodiment 1: owing to do not have RHEED on the pulsed laser deposition equipment, so after the si substrate temperature is raised to 600 ℃, use embodiment 1 the required time of RHEED diffraction fringe to occur, determine the time that beginning is grown continuously, use the excimer laser of output energy 280mJ, silicon temperature is elevated to 750 ℃, select the laser repetition rate of per second 6Hz for use with 25 minutes, at the mobile oxygen of the logical people 20Pa of epitaxial chamber, the thick La of preparation 500nm
0.7Sr
0.3MnO
3Film and La
0.7Sr
0.3MnO
3/ Si p-n heterojunction material.
Embodiment 15
Use the pulsed laser deposition method, LaMnO
3As resilient coating, the thick YBCO superconducting thin film of preparation 350nm on silicon substrate.
Pressing the method for embodiment 9 makes, with embodiment 9 different condition be: use the excimer laser of output energy 300mJ, silicon temperature be elevated to 850 ℃, select the laser repetition rate of per second 10Hz for use with 30 minutes, at the mobile oxygen of the logical people 100Pa of epitaxial chamber, LaMnO
3As resilient coating, the thick YBCO superconducting thin film of growth 500nm on silicon substrate.
Embodiment 16
Press the method for embodiment 8 and make, LaMnO
3As resilient coating, be substrate with n type single crystalline Si, with the n type Sr of high temperature sintering
0.8La
0.2TiO
3Target; The Sr that epitaxial growth 300nm is thick
0.8La
0.2TiO
3Film and Sr
0.8La
0.2TiO
3/ Si n-n heterojunction material.
Embodiment 17
Press the method for embodiment 8 and make, LaMnO
3As resilient coating, the thick Ba of epitaxial growth 300nm in n type Si substrate
0.8La
0.2TiO
3Film and Ba
0.8La
0.2TiO
3/ Si n-n heterojunction material.
With n type Sr
0.8La
0.2TiO
3The high temperature sintering target replaces BaTiO
3Target is pressed embodiment 8 concrete steps, epitaxial growth LaMnO
3The layer as resilient coating, the thick Ba of epitaxial growth 300nm in the Si substrate
0.8La
0.2TiO
3Film and Ba
0.8La
0.2TiO
3/ Si n-n heterojunction material.
Embodiment 18
Press the method for embodiment 8 and make, LaMnO
3As resilient coating, the thick Sr of epitaxial growth 200nm in n type Si substrate
0.8In
0.2TiO
3Film and Sr
0.8In
0.2TiO
3/ Si p-n heterojunction material.
With p type Sr
0.8In
0.2TiO
3The high temperature sintering target replaces BaTiO
3Target is pressed the preparation of embodiment 8 concrete steps, LaMnO
3As resilient coating, the thick Sr of epitaxial growth 200nm in the Si substrate
0.8In
0.2TiO
3Film and Sr
0.8In
0.2TiO
3/ Si p-n heterojunction material.
Embodiment 19
Press the method for embodiment 8 and make, LaMnO
3As resilient coating, the thick Ba of epitaxial growth 200nm in n type Si substrate
0.8In
0.2TiO
3Film and Ba
0.8In
0.2TiO
3/ Si p-n heterojunction material.
With p type Ba
0.8La
0.2TiO
3The high temperature sintering target replaces BaTiO
3Target is pressed embodiment 8 methods, LaMnO
3As resilient coating, the thick Ba of epitaxial growth 200nm in the Si substrate
0.8In
0.2TiO
3Film and Ba
0.8In
0.2TiO
3/ Si p-n heterojunction material.
Claims (11)
1. epitaxial growth iron-based alloy thin films and heterojunction materials on silicon chip comprises following composition:
With n type silicon chip is substrate;
The iron-based alloy La of growth one deck p type on its n type silicon chip substrate
1-xA
xMnO
3Film forms the p-n heterojunction material simultaneously; Wherein A is: Ca, Sr, Ba, Pb or Sn, the span of all x is 0.05～0.5.
2. epitaxial growth iron-based alloy thin films and heterojunction materials on silicon chip comprises following composition:
With p type silicon chip is on the substrate;
The iron-based alloy La of growth one deck p type on its p type silicon chip substrate
1-xA
xMnO
3Film forms the p-p heterojunction material simultaneously; Wherein A is: Ca, Sr, Ba, Pb or Sn, the span of all x is 0.05～0.5.
3. epitaxial growth iron-based alloy thin films and heterojunction materials on silicon chip comprises following composition:
With p type silicon chip is on the substrate;
The iron-based alloy La of growth one deck n type on its p type silicon chip substrate
1-xB
xMnO
3Thin-film material forms the p-n heterojunction material simultaneously; Wherein B is: Ce, Pr, Te, Nb, Sb or Ta, the span of all x is 0.05～0.5.
4. epitaxial growth iron-based alloy thin films and heterojunction materials on silicon chip comprises following composition:
With n type silicon chip is substrate;
The iron-based alloy La of growth one deck n type on its n type silicon chip substrate
1-xB
xMnO
3Thin-film material forms the n-n heterojunction material simultaneously; Wherein B is: Ce, Pr, Te, Nb, Sb or Ta, the span of all x is 0.05～0.5.
By in the claim 1,2,3 or 4 each described on silicon chip epitaxial growth iron-based alloy thin films and heterojunction materials, it is characterized in that, also be included in the lanthanum manganate that prepared on the silicon substrate and iron-based alloy thin layer as resilient coating, the other one deck of epitaxial growth thereon forms p-n-p or n-p-n heterojunction material again; Or multilayer n-p-n-p-n-p perovskite oxide film.
By right want 5 described on silicon chip epitaxial growth iron-based alloy thin films and heterojunction materials, it is characterized in that described perovskite oxide comprises: YBCO, BaTiO
3, LaAlO
3, SrTiO
3And the BaTiO that mixes
3, SrTiO
3
By right want 6 described on silicon chip epitaxial growth iron-based alloy thin films and heterojunction materials, it is characterized in that the BaTiO of described doping
3Comprise: n type barium titanate BaA
xTi
1-xO
3Or Ba
1-xLa
xTiO
3Thin-film material, wherein A is Nb or Ta; P type barium titanate BaB
xTi
1-xO
3, wherein B is In or Ga or Mn.The span of all x is 0.005～0.5.
By right want 6 described on silicon chip epitaxial growth iron-based alloy thin films and heterojunction materials, it is characterized in that the SrTiO of described doping
3Comprise: n type strontium titanates SrA
xTi
1-xO
3Or Sr
1-xLa
xTiO
3Thin-film material, wherein A is Nb or Ta; P type strontium titanates SrB
xTi
1-xO
3, wherein B is In or Ga or Mn.The span of all x is 0.005～0.5.
One kind prepare in the claim 1,2,3 or 4 each described on silicon chip the method for epitaxial growth iron-based alloy thin films and heterojunction materials, be included in laser molecular beam epitaxy or the pulsed laser deposition device, carry out according to the following steps:
(1). select the lanthanum manganate or the composite mixed lanthanum manganate target of high temperature sintering for use, the target of described p type is iron-based alloy La
1-xA
xMnO
3, wherein A is: Ca, Sr, Ba, Pb or Sn, and the span of all x is 0.05～0.5;
The target of described n type is iron-based alloy La
1-xB
xMnO
3, wherein B is: Ce, Pr, Te, Nb, Sb or Ta, and the span of all x is 0.05～0.5;
(2). selecting n type or p type silicon chip after (100) alignment surfaces is polished for use is substrate;
(3). the selected backing material of step 2 is carried out the silicon chip chemical cleaning of semiconductor standard, the silicon chip after cleaning up is directly taken out from the hydrofluoric acid washing lotion; Perhaps select the silicon chip of exempting to clean for use, silicon chip in the hydrofluoric acid washing lotion after the rinsing, and in the Sample Room or epitaxial chamber in the epitaxial apparatus of packing at once;
(4). after silicon chip is put into epitaxial chamber, epitaxial chamber's vacuum degree is evacuated to is better than 1 * 10
-2Pa carries out epitaxial growth; At first in the temperature range of room temperature to 400 ℃, use pulsed laser deposition, the iron-based alloy of 1～20 primitive unit cell layer of sputter on silicon chip;
(5) there is the silicon chip of 1～20 primitive unit cell layer iron-based alloy on the surface that step (4) sputter is obtained, be heated to 450 ℃～750 ℃, observe with reflection high energy electron diffraction, after the diffraction fringe that observes iron-based alloy occurs, with regard to aerating oxygen and continuous epitaxial growth iron-based alloy film;
(6) after Zhi Bei thickness reaches requirement, stop laser splash, the mobile oxygen when keeping growth is reduced to room temperature to sample temperature, takes out sample from epitaxial chamber then, and preparation process is finished.
By claim 9 described on silicon chip the method for epitaxial growth iron-based alloy thin films and heterojunction materials, it is characterized in that: described is silicon chip rinsing time in the hydrofluoric acid washing lotion 1 second-5 minute.
11. by claim 9 described on silicon chip the method for epitaxial growth iron-based alloy thin films and heterojunction materials, it is characterized in that: pressing to epitaxial chamber's aerating oxygen in the described step (5) is 2 * 10
-4Pa～100Pa's, and with the frequency continuous emission excimer laser pulse of 1～10Hz.
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