CN1416157A - Method for preparing nano-scale ordered microcrack on strontium titanate substrate - Google Patents
Method for preparing nano-scale ordered microcrack on strontium titanate substrate Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 26
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title description 3
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000004544 sputter deposition Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 70
- 238000000992 sputter etching Methods 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 238000001771 vacuum deposition Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 230000002269 spontaneous effect Effects 0.000 claims description 4
- 238000012876 topography Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910002367 SrTiO Inorganic materials 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000004549 pulsed laser deposition Methods 0.000 claims description 3
- 241000931526 Acer campestre Species 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 208000037656 Respiratory Sounds Diseases 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HEOGEEMADXKTBU-UHFFFAOYSA-N [O].[Mn].[Ca].[La] Chemical compound [O].[Mn].[Ca].[La] HEOGEEMADXKTBU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000000233 ultraviolet lithography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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Abstract
The invention belongs to the field of nano-structure preparation. The LCMO thin film is deposited on the STO substrate through laser sputtering, the self-organization behavior of the LCMO thin film in the heat treatment process is utilized, and the nanometer orthogonal ordered micro-crack structure is formed on the surface of the LCMO thin film spontaneously through controlling the deposition temperature, the annealing temperature, the thickness of the thin film and other process conditions in the preparation process, so that the purpose of preparing the nanometer ordered micro-structure on the STO substrate is achieved. The method has the advantages of simple and reliable process, easy control, good sample repeatability and low equipment requirement. The present invention, as a general technique, will find wide application in a variety of fields.
Description
The invention belongs to the nanostructure preparation field.
The preparation of nanostructure has very important meaning.On the one hand, the characteristic dimension of nanostructure is 1～100nm, the interfacial effect of material, the dimensional effect highly significant that becomes in this range scale, can produce some unusual performances and new rule, as quantum size effect, skin effect and macro quanta tunnel effect etc., this is significant aspect theory research.On the other hand, nanostructure, submicrometer structure can be widely used in photoelectric cell, and (Science 264,48 (1994) for document 1, B.C.Bunker et al. as filter, optoelectronic switch, light sensitive component etc.; Document 2, C.B.Roxlo et al., Science 235,1629 (1987); Document 3, S.Hazashiet al., J.Colloid Interface Sci.144,538 (1991); Document 4, F.Burmeisteret al., Langmuir 13,2983 (1997); Document 5, C.Padeste et al., J.Electrochem.Soc.143,3890 (1996)), therefore have important use to be worth.People have been developed the preparation that a lot of methods realize nanostructure, submicrometer structure, as (documents 6 such as " Contact " photoetching technique, " Nanoimprint " mechanical technology, the micro-delineation technology of atomic force, ultraviolet lithographies, James G.Goodberlet, Appl.Phys.Lett.76,667 (2000); Document 7, Ingo Martini, Dominik Eisert, Martin Kamp, LukasWorschech, Alfred Forchel and Johannes Koeth, Appl.Phys.Lett.77,2237 (2000); Document 8, C.K.Hyon, S.C.Choi, S.-H.Song, S.W.Hwang, M.H.Son, D.Ahn, Y.J.Park and E.K.Kim, Appl.Phys.Lett.77,2607 (2000); Document 9, Susanne Friebel, Joanna Aizenberg, Silvia Abad, and Pierre Wiltzius, Appl.Phys.Lett.77,2406 (2000)).But these methods are all used complicated etching technics inevitably or equipment are had higher requirement.Utilize the self-organizing characteristic of material prepare the microcosmic ordered structure be a kind of simple directly, efficient ways, can avoid above-mentioned inconvenience, this seems in the preparation of microcircuit and is even more important.
The objective of the invention is to overcome the shortcoming and defect of prior art, utilize lanthanum calcium manganese oxygen (La in the heat treatment process
xCa
1-xMnO
3, LCMO) the self-organizing behavior of film reaches single-crystal strontium titanate (SrTiO in the LCMO film
3, STO) spontaneous formation nanoscale quadrature ordered microcrack structure on the substrate, thus reach the purpose that on the STO substrate, prepares nano ordered micro-structural.Simple and reliable process of the present invention is easy to control, the sample good reproducibility, and equipment requirements is low.Since monocrystalline STO as substrate in film preparation, especially in the preparation of superconducting thin film, ferroelectric thin film, giant magnetoresistive thin film, semiconductive thin film and multilayer film, have very widely and to use, so the present invention also will be widely used in the basic research in these fields and application study as a kind of current techique.
The object of the present invention is achieved like this:
The present invention adopts the laser splash method to deposit the LCMO film on the STO substrate, utilize the difference of LCMO film and STO substrate thermal coefficient of expansion, by the process conditions such as depositing temperature, annealing temperature and film thickness in the control film preparation process, make the spontaneous formation nanoscale of LCMO film surface quadrature ordered microcrack structure (see figure 1).These micro-crack width run through whole LCMO thin layer less than 5 nanometers, and extend in the STO substrate, make also to have formed corresponding nanoscale quadrature ordered microcrack structure (see figure 2) on the STO substrate.Therefore, only need to adopt the ion etching technology that the LCMO thin layer on this sample is peeled off, can on the STO substrate, obtain nanoscale quadrature ordered microcrack structure (see figure 3).Simultaneously, ion etching technology can not destroyed the surface crystal structure (see figure 4) of STO substrate, and the STO after etching still can be used as substrate and is suitable for various uses.
Introduce preparation method of the present invention below in detail:
At first, adopt the method for laser splash deposition to prepare the LCMO film that the surface has nanoscale quadrature ordered microcrack on the STO substrate, the technological factor that influences micro-cracked structure mainly contains depositing temperature, film thickness and annealing temperature.
The selection of depositing temperature has determined the primary crystallization situation of LCMO film, directly has influence on the size of rete and substrate interface stress.Depositing temperature is low excessively, and the thin film crystallization situation is bad, and stress is discharged by polycrystalline grain crystal boundary or amorphous component, ordered microcrack can not occur on rete and the substrate; Depositing temperature is too high, and big crystal grain appears in film surface easily, also ordered microcrack can not occur.Experiment showed, when depositing temperature is 750～800 ℃ that the ordered microcrack structure is easy to occur on the LCMO film.
Micro-crack is produced by the driving of film internal stress, and the film internal stress then is that the difference by lattice constant and thermal coefficient of expansion between LCMO film and the STO substrate causes, so annealing in process is the committed step of micro-crack generation.Only under suitable heat treatment temperature, film, substrate just ordered microcrack can occur.When experimental results show that annealing temperature less than 850 ℃, the micro-cracked structure of film surface can not generate.When annealing temperature was 850～900 ℃, micro-cracked structure generated easily.In this temperature range, annealing temperature is low more, and the width of crackle is more little, and density is low more; Otherwise then the width of crackle is big more, and density is high more.But when heat treatment temperature during, will cause face coarse, big crystalline particle occur greater than 900 ℃.
Film thickness and film internal stress can accumulate direct relation, it can be by controlling the adjustment of laser energy, laser frequency, sputtering time, sputtering pressure.The laser energy that adopts in the experiment is 550mJ, and laser frequency is 5Hz, and sputtering pressure is 50Pa.With this understanding, the energy density that produces on target surface of laser is about 2.0J/mm
2, the depositing of thin film rate is about 20 nm/minute.Therefore, according to depositing of thin film speed, can choose suitable sputtering time and realize control film thickness.When thickness during less than 80 nanometers, film internal stress deficiency is so that film produces micro-crack; When thickness was 80～160 nanometers, the film internal stress accumulated along with the increase of thickness, and orderly micro-cracked structure appears in film, and its density increases (about 1000/mm along with the increase of film thickness
2Article～25000 ,/mm
2); When thickness during greater than 160 nanometers, owing to be easy to produce big crystal grain in the film, thus produce a large amount of crystal boundaries, discharge stress, ordered microcrack is difficult for generating.
After having prepared LCMO film, adopt ion etching technology that the LCMO thin layer is peeled off and just can on the STO substrate, make corresponding nanoscale quadrature ordered microcrack structure with special appearance structure.The air pressure that adopts during ion etching is 1.5～4.0 * 10
-2Pa, the etching energy of ions is 450～550eV, ion beam current density is 35～45mA/cm
2, the etching inclination angle is 20～30 °, the etch rate of film is about 10 nm/minute with this understanding.After the etching 10～20 minutes, the LCMO film is stripped from, and just leaves corresponding ordered microcrack structure on the STO substrate, and the width of crackle is relevant with the etching degree, usually less than 100 nanometers.
The present invention must be in order to down equipment and material: equipment requirements: 1 ultrasonic cleaning instrument (index is not done special requirement);
2 pulsed laser sources: the KrF laser of the LPX 300cc type that Lambda Physik company produces, optical maser wavelength is 248 nanometers, pulse duration was 25 nanoseconds;
3 vacuum coating equipments: final vacuum is 5.0 * 10
-4Pa, 1000 ℃ of chip bench maximum heating temperatures, target spacing 4.0～4.7cm;
The supporting vacuum pump of 4 vacuum coating equipments: first order vacuum pump: the mechanical pump speed of exhaust is 8 L/s, and limiting pressure is 6 * 10
-2Pa, second level vacuum pump: the molecular pump speed of exhaust is 600L/s, limiting pressure is 1 * 10
-8Pa;
The supporting temperature controller of 5 vacuum coating equipments: the SR50 type single loop process adjuster of day island proper electricity company production;
6 ion etching equipments: final vacuum is 5.0 * 10
-4Pa;
The supporting vacuum pump of 7 ion etching equipments: first order vacuum pump: the mechanical pump speed of exhaust is 8L/s, and limiting pressure is 6 * 10
-2Pa, second level vacuum pump: the molecular pump speed of exhaust is 600L/s, limiting pressure is 1 * 10
-8Pa.Material requirements: analyze absolute alcohol, analyze pure acetone, deionized water,
(100) Qu Xiang SrTiO
3(STO) substrate, single-sided polishing,
High purity oxygen gas, high-purity argon gas,
La
0.5Ca
0.5MnO
3(LCMO) target.Detection means: 1 step calibrator is surveyed thicknesses of layers; 2 X-ray survey the crystal structure of film;
3 atomic force microscope (AFM) are surveyed the surface topography of film and substrate;
4 transmission electron microscopes (TEM) are done the cross section of film and are covered the lining picture.
The present invention realizes by following steps:
1) clean substrate:
The STO substrate successively is dipped in acetone and the alcohol, carries out ultrasonic cleaning repeatedly, until its polished surface cleaning, the perusal contamination-free gets final product, and uses washed with de-ionized water at last.
2) preparation LCMO film:
The substrate that cleaned oven dry back is sticked at elargol on the chip bench of coating chamber and prepares deposition, coating chamber is vacuumized, simultaneously with 1000～1500 ℃/hour speed heated substrate platform to 750～800 ℃ of depositing temperatures.When the vacuum degree of coating chamber less than 4.0 * 10
-3Pa and chip bench continue to charge into high purity oxygen gas (throughput is regulated with the ultra high vacuum angle valve, and concrete numerical value is not done special requirement, exceeds with the molecular pump nonoverload) with certain throughput when depositing temperature place constant temperature, make vacustat at 30～70Pa.Carry out pulsed laser deposition subsequently, used pulse laser parameter area is as follows: laser energy is 400～600mJ/ pulse; Laser frequency is 3～8Hz; Laser energy density is 1.2～2.0J/cm
2The about 2mm of spot size on the target
2With this understanding, LCMO depositing of thin film rate is about 20nm/min.Deposition rate is chosen the sputtering time of 4～8min and can be prepared the LCMO film that thickness is 80～160nm in view of the above.
3) further heat treatment:
After sputter finishes, charge into high purity oxygen gas fast, make the coating chamber internal gas pressure reach 8,000～10, about 000Pa; With 400～600 ℃/hour speed heated substrate platform, make its temperature reach 850～900 ℃, and under this temperature constant temperature 10～30min; After cooled to room temperature in 2～3 hours.
The LCMO film surface that adopts above step to make has the quadrature ordered microcrack structure of the nanoscale of spontaneous formation.
4) ion etching:
The above LCMO film sample for preparing is put on the sample stage of etch chamber, vacuumizes.When vacuum degree reaches 1.1 * 10
-3During Pa, continue to charge into high-purity argon gas, make vacuum degree remain on 1.5～4.0 * 10
-2Pa.Rotation and refrigeration sample stage make sample stage tilt to become 20～30 ° of angles with incident ion simultaneously, begin etching then.The ion energy that adopts is 450～550eV, and beam current density is 35～45mA/cm
2, the etch rate of film is 10nm/min with this understanding.According to film thickness etching 10～20 minutes, can obtain the STO substrate that the surface has the nano ordered microcrack structure, the micro-crack width is less than 100nm.
The present invention can be on the STO substrate than large tracts of land in the micro-structural (less than 100nm) of (relevant) preparation nanoscale with chip area, little 1～2 order of magnitude of yardstick that this scale ratio photoetching process commonly used can reach.The sample of the present invention's preparation can be widely used in the basis and the application study in fields such as superconducting thin film, super large magneto-resistor film, ferroelectric thin film, semiconductor, heterojunction.The present invention is simple for process, the STO substrate that adopts this method preparation to have nanoscale quadrature ordered microcrack structure, only need when preparation LCMO film laser splash parameter and temperature controlled and get final product, adopt the method for ion etching to peel off the LCMO thin layer then, need not acid etching, other supplementary means such as photoetching.Good reliability of the present invention, sample repeatability better, the thickness of film, depositing temperature and heat treatment temperature have a direct impact the situation of micro-crack, and have certain corresponding relation with the width and the density of crackle.Film thickness can be controlled preferably by the laser splash parameter.The accurate control of depositing temperature and heat treatment temperature also more easily realizes by temperature controlling instruments.
The present invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is atomic force microscope (AFM) the surface topography picture of the LCMO film of surface with nanoscale quadrature ordered microcrack structure.
Fig. 2 is the cross section diffraction contrast image of the perspective electron microscope of micro-crack in the LCMO film.As seen from the figure, the micro-crack width in the LCMO film is less than 5nm, and the crack penetration thin layer also extends in the STO substrate.
Fig. 3 (a) is after the method for employing ion etching is peeled off the LCMO film, has the AFM surface topography picture of the STO substrate of nanoscale quadrature ordered microcrack structure, and figure (b) and figure (c) are line analysis, the surface analysis result of micro-crack.STO among the figure (a) representative is through the STO of ion etching substrate; STO (b) representative is without the substrate of ion etching.As seen from the figure, the on-chip micro-crack width of STO is 100nm, and the surperficial average flatness of STO substrate is not subjected to the influence of ion etching technology substantially.
Fig. 4 is through ion etching and the analysis that relatively reaches the AFM surface appearance without the X-ray diffraction result of the STO substrate of ion etching.Wherein STO (a) is identical with implication and Fig. 3 of STO (b), and the STO+LCMO representative deposits the STO substrate of LCMO film.As seen from the figure, ion etching does not have obvious influence to the crystal structure and the surface appearance of STO substrate, and STO still can be used as substrate and is applicable to various uses after the etching.
Fig. 5 (a) is the AFM shape appearance figure of the different LCMO film of thickness with Fig. 5 (b), and wherein figure (a) film thickness is 120nm, and micro-crack density is about 10
4/ mm
2Figure (b) film thickness is 80nm, and micro-crack density is 10
3/ mm
2As seen, by can control the density of micro-crack indirectly to the selection of film thickness.Fig. 5 (c) is after the LCMO thin layer is peeled off, the nanoscale quadrature ordered microcrack structure that stays on the STO substrate.
Embodiment 1:
With 4 * 5mm
2(100) Qu Xiang monocrystalline STO is a substrate.After with alcohol, acetone substrate being cleaned cleaning repeatedly, adopt pulsed laser deposition deposition LCMO film, concrete process conditions are as follows: with 1000 ℃/hour heating rates chip bench is warming up to 800 ℃ of sputter temperature, simultaneously vacuum at the bottom of the back of the body of system is evacuated to 4.0 * 10
-3About Pa, feed the oxygen that flows then, and system's internal gas pressure is remained on 50Pa.Can carry out laser splash behind the system stability, pulsed laser energy is 550mJ, and pulse frequency is 5Hz, and LCMO depositing of thin film rate is 20nm/min, and sputtering time is 6min, and the LCMO thickness that obtains like this is about 120nm.After sputter finishes, charge into high purity oxygen gas fast, make intrasystem air pressure reach 8000～10,000Pa, and chip bench is warming up to 870 ℃ with 400 ℃/hour heating rate, 20min anneals under this temperature.At last chip bench is reduced to room temperature with 450 ℃/hour rate of temperature fall.Can make the LCMO film with quadrature ordered microcrack by above step, see Fig. 5 (a), the density of micro-crack is about 10
4/ mm
2
Embodiment 2:
Adopt and embodiment 1 described identical step, only change the sputtering time in the technological parameter into 4min, can obtain the LCMO film that thickness is about 80nm.The density that this film produces micro-crack is lower, is about 10
3/ mm
2, see Fig. 5 (b).This shows, can control the density of micro-crack indirectly by the thickness of selecting the LCMO film.
Adopt the method for ion etching that the LCMO thin layer of this sample is peeled off.At first the above-mentioned LCMO film sample for preparing is put on the sample stage of etch chamber, vacuumizes.When back of the body end vacuum degree reaches 1.1 * 10
-3During Pa, charge into mobile high-purity argon gas, make vacuum degree remain on 2.0 * 10
-2Pa.Rotation and refrigeration sample stage make sample stage tilt to become 25 ° of angles with incident ion simultaneously, begin etching then.The ion energy that adopts is 500eV, and beam current density is 40mA/cm
2, the etch rate of film is 10nm/min with this understanding.According to film thickness etching 15 minutes, can obtain the STO substrate that the surface has the nano ordered microcrack structure, the micro-crack width is seen Fig. 5 (c) less than 100nm.
Claims (1)
1. method for preparing nano ordered microcrack is characterized in that:
Equipment needed thereby, material and detection means are as follows:
1) equipment requirements: ultrasonic cleaning instrument, index are not done special requirement; The LPX 300cc type KrF laser that pulsed laser source is produced for LambdaPhysik company, optical maser wavelength is 248nm, pulsewidth 25ns; Vacuum coating equipment, its final vacuum are 5.0 * 10
-4Pa, 1000 ℃ of chip bench maximum heating temperatures, target spacing 4.0 ~ 4.7cm; The supporting vacuum pump of vacuum coating equipment: first order vacuum pump is a mechanical pump, speed of exhaust 8L/s, limiting pressure 6 * 10
-2Pa, second level vacuum pump are molecular pump, speed of exhaust 600L/s, limiting pressure 1 * 10
-8Pa; The supporting temperature controller of vacuum coating equipment is day SR50 type single loop process adjuster of island proper electricity company production; The final vacuum of ion etching equipment is 5.0 * 10
-4Pa; The supporting vacuum pump of ion etching equipment is with the supporting vacuum pump of above-mentioned vacuum coating equipment;
2) material requirements: analyze absolute alcohol, analyze pure acetone, deionized water; (100) Qu Xiang SrTiO
3(STO) substrate, single-sided polishing; High purity oxygen gas, high-purity argon gas; La
0.5Ca
0.5MnO
3(LCMO) target;
3) detection means: the step calibrator is surveyed thicknesses of layers; X-ray surveys the crystal structure of film; Atomic force microscope (AFM) is surveyed the surface topography of film and substrate; Transmission electron microscope (TEM) is done the cross section of film and is covered the lining picture;
May further comprise the steps:
1) cleans substrate: the STO substrate successively is dipped in analyzes in pure acetone and the analysis absolute alcohol, carry out ultrasonic cleaning repeatedly, till its polished surface cleaning, perusal contamination-free, use washed with de-ionized water at last;
2) preparation LCMO film: the substrate oven dry back that will clean sticks at elargol that preparation deposits on the chip bench of coating chamber; Coating chamber is vacuumized, simultaneously with 1000～1500 ℃/hour speed heated substrate platform to 750～800 ℃ of depositing temperatures; Vacuum degree is less than 4.0 * 10 at the bottom of the back of the body of coating chamber
-3Pa and chip bench continue to charge into high purity oxygen gas with certain throughput when depositing temperature place constant temperature; Throughput is regulated with the ultra high vacuum angle valve, and numerical value exceeds with the molecular pump nonoverload; Make vacustat at 30～70Pa; Carry out pulsed laser deposition subsequently, used pulse laser parameter area is as follows: laser energy is 400～600mJ/ pulse; Laser frequency is 3～8Hz; Laser energy density is 1.2～2.0J/cm
2The about 2mm of spot size on the target
2With this understanding, about 20 nm/minute of LCMO depositing of thin film rate are chosen the LCMO film that 4～8 minutes sputtering time can be prepared thickness 80～160 nanometers;
3) further heat treatment: after sputter finishes, charge into high purity oxygen gas fast, make the coating chamber internal gas pressure reach 8,000～10, about 000Pa; With 400～600 ℃/hour speed heated substrate platform, make its temperature reach 850～900 ℃, and under this temperature constant temperature 10～30 minutes; After cooled to room temperature in 2～3 hours; The LCMO film surface that makes thus has the quadrature ordered microcrack structure of the nanoscale of spontaneous formation;
4) ion etching: will more than the LCMO film sample for preparing be put on the sample stage of etch chamber and vacuumize, when vacuum degree reaches 1.1 * 10
-3During Pa, continue to charge into high-purity argon gas, make vacuum degree remain on 1.5～4.0 * 10
-2Pa; Rotation and cooling sample stage make sample stage tilt to become 20～30 ° of angles with incident ion simultaneously, begin etching then; The ion energy that adopts is 450～550eV, and beam current density is 35～45mA/cm
2, the etch rate of film is 10 nm/minute with this understanding; According to film thickness etching 10～20 minutes, can obtain the STO substrate that the surface has the nano ordered microcrack structure, gained micro-crack width is less than 100 nanometers.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103645078A (en) * | 2013-12-05 | 2014-03-19 | 广东工业大学 | Rapid cross section manufacture and sub-surface micro-crack detection method of single crystal semiconductor substrate |
| US8755582B2 (en) | 2008-12-10 | 2014-06-17 | Siemens Aktiengesellschaft | Method and device to determine distortion correction data |
| CN111785832A (en) * | 2020-07-10 | 2020-10-16 | 西安交通大学 | High-resolution low-temperature flexible strain resistance switch and preparation method thereof |
-
2001
- 2001-10-29 CN CN 01134312 patent/CN1188897C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8755582B2 (en) | 2008-12-10 | 2014-06-17 | Siemens Aktiengesellschaft | Method and device to determine distortion correction data |
| CN103645078A (en) * | 2013-12-05 | 2014-03-19 | 广东工业大学 | Rapid cross section manufacture and sub-surface micro-crack detection method of single crystal semiconductor substrate |
| CN103645078B (en) * | 2013-12-05 | 2016-01-20 | 广东工业大学 | A kind of cross section quick Fabrication of single crystal semiconductor substrate and sub-crizzle detection method |
| CN111785832A (en) * | 2020-07-10 | 2020-10-16 | 西安交通大学 | High-resolution low-temperature flexible strain resistance switch and preparation method thereof |
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| CN1188897C (en) | 2005-02-09 |
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