CN104726847B - Preparation method of gadolinium cuprate film - Google Patents
Preparation method of gadolinium cuprate film Download PDFInfo
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- CN104726847B CN104726847B CN201510143684.5A CN201510143684A CN104726847B CN 104726847 B CN104726847 B CN 104726847B CN 201510143684 A CN201510143684 A CN 201510143684A CN 104726847 B CN104726847 B CN 104726847B
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Abstract
The invention relates to a preparation method of a gadolinium cuprate film, which comprises the following steps: (1) putting a strontium titanate substrate onto a substrate seat in a chemical vapor deposition reaction chamber; (2) weighing a gadolinium source and a copper source as solid raw materials, and respectively putting the two raw materials in corresponding raw material tanks; (3) heating the substrate seat to 1040-1120 DEG C, respectively heating the raw material tanks to 220-230 DEG C and 180-200 DEG C; (4) introducing current carrying gas containing a gadolinium source and a copper source and oxidizing gas into the reaction chamber to react; and (5) stopping introducing gas, shutting down the heating system, and cooling to room temperature to obtain the gadolinium cuprate film deposited on the strontium titanate substrate. Compared with the prior art, the method has the advantages of high film-forming speed, short reaction time, high production efficiency and controllable structure. Compared with the non-oriented Gd2CuO4 film, the (001)-oriented Gd2CuO4 film has special crystal structure and physical properties.
Description
Technical field
The present invention relates to a kind of technology of preparing of copper acid gadolinium thin film, prepares especially with chemical vapour deposition technique
(001) the copper acid gadolinium thin film being orientated, belongs to film material with function preparation field.
Background technology
The group of the lanthanides Cu oxide RE of Ce and Th doping2-xMxCuO4(RE=Pr, Nd, Sm and Eu；M=Ce and Th) tool
There is superconducting property.Research shows that its supercurrent carrier is electronics, different from the YBa that carrier is hole2Cu3O7-δTradition
Superconductor.Its crystal structure is the Nd with Cu-O planar structures2CuO4(T ') structure, different from Cu-O pyramids
The YBa of structure2Cu3O7-δConventional superconductors.Because of its special crystal structure and physical property, RE2-xMxCuO4Cause extensive
Research.
Gd2CuO4With RE2-xMxCuO4With identical crystal structure, and with more special physical property and extensively
Application prospect.First, having the Gd of T ' structures2CuO4Various magnetic property with complexity；Second, (001) is orientated
Gd2CuO4Thin film has superconductivity, and its critical transition temperature is 19K；Third, due to Gd2CuO4With photoelectricity, magneto-optic, superconduction
And catalysis etc. characteristic, before the aspects such as microelectronics, opto-electronic device, superconductive device, catalyst, sensor have a wide range of applications
Scape.Such as adulterate the La of Ce2-xCexCuO4Can be used as the three-way catalyst of purifying vehicle exhaust；The Gd of doping Sr2-xSrxCuO4Can
Catalyst as NO Direct Resolutions；Gd2CuO4Material can be used as NO, CO and NO2Deng the sensor of gas；Gd2CuO4Thin film is made
The structure of ferroelectric thin film can be improved for hearth electrode material and the service behaviour of ferro-electric device is improved.
At present, both at home and abroad for Gd2CuO4The preparation of block materials there has been many researchs, but for Gd2CuO4Thin film
Research is less, and preparation method mostly is physical vaporous deposition.
Gd is prepared at present2CuO4In the common method of thin film, PLD and multi-source coevaporation method sedimentation rate are low, and with thin
The increase of film thickness, crystalline quality can also produce larger decline.MOD methods prepare the presoma required for thin film and prepare and constitute
Control is relatively difficult, and needs to be repeated several times when thick film is prepared to smear deposition, low production efficiency.
Chemical vapour deposition technique is preparing Gd as a kind of important method for preparing thin-film material2CuO4In terms of thin film also not
Appear in the newspapers.The characteristics of chemical vapour deposition technique has sedimentation rate height, low vacuum level requirements, organizational structure and controllable thickness.Cause
This, prepares Gd using chemical vapour deposition technique2CuO4Thin film is with control material structure for the mechanism of its magnetic, superconductivity is ground
Study carefully and industrialized production is significant.
The content of the invention
The technical problem to be solved is：A kind of preparation method of copper acid gadolinium thin film, prepared copper acid are provided
The out-of-plane orientation of gadolinium thin film is fully oriented for (001).
In order to solve its technical problem, the technical solution adopted in the present invention is：A kind of preparation method of copper acid gadolinium thin film,
Comprise the following steps：
(1) strontium titanates substrate is put in the substrate holder in chemical vapour deposition reaction cavity, and by the pressure in cavity
It is evacuated to below 30Pa；
(2) gadolinium source and copper source solid material is weighed, two kinds of raw materials is respectively placed in corresponding head tank；Described gadolinium source
Three (DPM dpm,dipivalomethane acid) gadoliniums and double (DPM dpm,dipivalomethanes are respectively with copper source
Acid) copper；
(3) temperature of substrate holder is risen to into 1040～1120 DEG C, the head tank temperature in gadolinium source and copper source is risen to into 200 respectively
～230 DEG C and 180～200 DEG C；
(4) the current-carrying gas containing gadolinium source and copper source and oxic gas are passed through in reaction cavity, adjust the pressure in cavity
To 300～500Pa, the response time is 7～10min；
(5) stop being passed through gas, close heating system, be cooled to room temperature, that is, obtain the copper being deposited on strontium titanates substrate
Sour gadolinium thin film.
By such scheme, described strontium titanates substrate makes its clean surface through pretreatment.
By such scheme, described preprocess method is：Substrate is placed in into supersound process in ethanol, is then dried up, ultrasound
Process time is 20～30min.
By such scheme, described current-carrying gas is argon, and oxic gas are oxygen.
By such scheme, described argon flow amount is 100～300sccm, and oxygen flow is 300～500sccm.
The principle of chemical vapour deposition technique of the present invention is：After solid feed is evaporated, by current-carrying fate
Defeated there is chemical reaction at high temperature in substrate surface in the gas absorption containing reaction raw materials in reaction cavity, generate solid-state
Thin film.By-product departs from surface, and is evacuated system and takes away.
Compared with prior art, the invention has the beneficial effects as follows：
1. thin film is prepared using chemical vapour deposition technique, compared to MOD, PLD and polynary coevaporation method, film forming speed
Hurry up, the response time is short, production efficiency is high and organizational structure is controllable.
2. the Gd that (001) is orientated2CuO4Gd of the thin film compared to No yield point2CuO4Thin film have special crystal structure and
Physical property, is expected to obtain in fields such as microelectronics, opto-electronic device, superconductive device, catalyst, sensor and electrode materials
It is widely applied.
Description of the drawings
Fig. 1 is the XRD spectrum of the copper acid gadolinium thin film prepared by the embodiment of the present invention, and wherein Fig. 1 (a) is the embodiment of the present invention
The XRD spectrum of the copper acid gadolinium thin film prepared by 1；Fig. 1 (b) is the XRD figure of the copper acid gadolinium thin film prepared by the embodiment of the present invention 2
Spectrum；Fig. 1 (c) is the XRD spectrum of the copper acid gadolinium thin film prepared by the embodiment of the present invention 3.
Fig. 2 is the surface SEM picture and section SEM pictures of the copper acid gadolinium thin film prepared by the embodiment of the present invention；Wherein Fig. 2
A () is the surface SEM pictures of the copper acid gadolinium thin film prepared by the embodiment of the present invention 1；Fig. 2 (b) is prepared by the embodiment of the present invention 2
Copper acid gadolinium thin film surface SEM pictures；Fig. 2 (c) is the surface SEM figures of the copper acid gadolinium thin film prepared by the embodiment of the present invention 3
Piece；Fig. 2 (d) is the section SEM pictures of the copper acid gadolinium thin film prepared by the embodiment of the present invention 1；Fig. 2 (e) is the embodiment of the present invention 2
The section SEM pictures of prepared copper acid gadolinium thin film；Fig. 2 (f) is the section of the copper acid gadolinium thin film prepared by the embodiment of the present invention 3
SEM pictures.
Specific embodiment
Present disclosure is further elucidated with reference to embodiment, but the present invention is not limited solely to following enforcement
Example.
In following embodiments, strontium titanates substrate makes its clean surface, preprocess method be through pretreatment：By strontium titanate base
Plate is placed in supersound process 30min in ethanol, then dries up standby.
Embodiment 1
(1) strontium titanates substrate is put in the substrate holder in chemical vapour deposition reaction cavity, and by the pressure in cavity
It is evacuated to below 30Pa；
(2) (DPM dpm,dipivalomethane acid) gadoliniums that weigh a certain amount of three and it is double (2,2,6,6- tetramethyls-
The acid of 3,5- heptadione) copper solid material, two kinds of raw materials are respectively placed in corresponding head tank；
(3) temperature of substrate holder is risen to into 1120 DEG C, by the head tank temperature in gadolinium source and copper source rise to respectively 220 DEG C and
192℃；
(4) argon and oxygen containing gadolinium source and copper source are passed through in reaction cavity, it is 100sccm to adjust argon flow velocity,
Oxygen gas flow rate is 300sccm, adjusts the pressure in cavity to 300Pa, and the response time is 10min；
(5) stop being passed through gas, close heating system, be cooled to room temperature, that is, obtain the copper being deposited on strontium titanates substrate
Sour gadolinium thin film.
As shown in Fig. 1 (a), there is (002) in the XRD diffracting spectrums of the copper acid gadolinium thin film prepared by embodiment 1, (004),
(006) and (008) diffraction maximum, show that the out-of-plane orientation of copper acid gadolinium thin film is fully oriented for (001).As shown in Fig. 2 (a), (d),
1 gained copper of embodiment acid gadolinium thin film is continuous, fine and close, about 0.555 micron of film thickness.Crystal grain is in needle-like and island growth, brilliant
Grain marshalling.
Embodiment 2
(1) strontium titanates substrate is put in the substrate holder in chemical vapour deposition reaction cavity, and by the pressure in cavity
It is evacuated to below 30Pa；
(2) (DPM dpm,dipivalomethane acid) gadoliniums that weigh a certain amount of three and it is double (2,2,6,6- tetramethyls-
The acid of 3,5- heptadione) copper solid material, two kinds of raw materials are respectively placed in corresponding head tank；
(3) temperature of substrate holder is risen to into 1080 DEG C, by the head tank temperature in gadolinium source and copper source rise to respectively 220 DEG C and
192℃；
(4) argon and oxygen containing gadolinium source and copper source are passed through in reaction cavity, it is 100sccm to adjust argon flow velocity,
Oxygen gas flow rate is 300sccm, adjusts the pressure in cavity to 300Pa, and the response time is 10min；
(5) stop being passed through gas, close heating system, be cooled to room temperature, that is, obtain the copper being deposited on strontium titanates substrate
Sour gadolinium thin film.
As shown in Fig. 1 (b), there is (002) in the XRD diffracting spectrums of the copper acid gadolinium thin film prepared by embodiment 2, (004),
(006) and (008) diffraction maximum, show that the out-of-plane orientation of copper acid gadolinium thin film is fully oriented for (001).As shown in Fig. 2 (b), (e),
2 gained copper of embodiment acid gadolinium thin film is continuous, fine and close, about 0.369 micron of film thickness.Crystal grain is in mainly island growth.
Embodiment 3
(1) strontium titanates substrate is put in the substrate holder in chemical vapour deposition reaction cavity, and by the pressure in cavity
It is evacuated to below 30Pa；
(2) (DPM dpm,dipivalomethane acid) gadoliniums that weigh three and double (2,2,6,6- tetramethyls -3,5- heptan two
Keto acid) copper solid material, two kinds of raw materials are respectively placed in corresponding head tank；
(3) temperature of substrate holder is risen to into 1040 DEG C, by the head tank temperature in gadolinium source and copper source rise to respectively 220 DEG C and
192℃；
(4) argon and oxygen containing gadolinium source and copper source are passed through in reaction cavity, it is 100sccm to adjust argon flow velocity,
Oxygen gas flow rate is 300sccm, adjusts the pressure in cavity to 300Pa, and the response time is 10min；
(5) stop being passed through gas, close heating system, naturally cool to room temperature, that is, obtain being deposited on strontium titanates substrate
Copper acid gadolinium thin film.
As shown in Fig. 1 (c), there is (002) and (004) and spread out in the XRD diffracting spectrums of the copper acid gadolinium thin film prepared by embodiment 3
Peak is penetrated, shows that the out-of-plane orientation of copper acid gadolinium thin film is fully oriented for (001).As shown in Fig. 2 (c), (f), the acid of 3 gained copper of embodiment
Gadolinium thin film is continuous, fine and close, about 0.195 micron of film thickness.Crystal grain is less, and film surface is more smooth.
Particular embodiments described above, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail.For a person skilled in the art, the present invention can have various modifications and variations, all spirit in the present invention
With any modification made in principle, equivalent, improvement etc., all should be in protection scope of the present invention.
Claims (5)
1. the preparation method of a kind of copper acid gadolinium thin film, it is characterised in that comprise the following steps：
(1) strontium titanates substrate is put in the substrate holder in chemical vapour deposition reaction cavity, and the pressure in cavity is evacuated to
Below 30Pa；
(2) gadolinium source and copper source solid material is weighed, two kinds of raw materials is respectively placed in corresponding head tank；Described gadolinium source and copper
Source is respectively three (DPM dpm,dipivalomethane acid) gadoliniums and double (DPM dpm,dipivalomethane acid) copper；
(3) temperature of substrate holder is risen to into 1040～1120 DEG C, the head tank temperature in gadolinium source and copper source is risen to into 200 respectively～
230 DEG C and 180～200 DEG C；
(4) the current-carrying gas containing gadolinium source and copper source and oxic gas are passed through in reaction cavity, the pressure in regulation cavity to 300
～500Pa, response time are 7～10min；
(5) stop being passed through gas, close heating system, be cooled to room temperature, that is, obtain the copper acid gadolinium being deposited on strontium titanates substrate
Thin film.
2. a kind of preparation method of copper acid gadolinium thin film according to claim 1, it is characterised in that described strontium titanates substrate
Its clean surface is made through pretreatment.
3. a kind of preparation method of copper acid gadolinium thin film according to claim 2, it is characterised in that described preprocess method
It is：Substrate is placed in into supersound process in ethanol, is then dried up, sonication treatment time is 20～30min.
4. the preparation method of a kind of copper acid gadolinium thin film according to claim 1, it is characterised in that described current-carrying gas is argon
Gas, oxic gas are oxygen.
5. the preparation method of a kind of copper acid gadolinium thin film according to claim 4, it is characterised in that described argon flow amount is
100～300sccm, oxygen flow are 300～500sccm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896305A (en) * | 2005-07-14 | 2007-01-17 | 中国科学技术大学 | Production of multifunctional gas-phase depositer and solid oxide fuel single cell |
| EP2233605A1 (en) * | 2000-12-12 | 2010-09-29 | Konica Corporation | Product comprising a metal oxide layer having a carbon content of from 0.1 to 5 % by weight, and optical film |
| CN102270738A (en) * | 2010-06-03 | 2011-12-07 | 北京大学 | Manufacturing method of memory unit comprising resistor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2233605A1 (en) * | 2000-12-12 | 2010-09-29 | Konica Corporation | Product comprising a metal oxide layer having a carbon content of from 0.1 to 5 % by weight, and optical film |
| CN1896305A (en) * | 2005-07-14 | 2007-01-17 | 中国科学技术大学 | Production of multifunctional gas-phase depositer and solid oxide fuel single cell |
| CN102270738A (en) * | 2010-06-03 | 2011-12-07 | 北京大学 | Manufacturing method of memory unit comprising resistor |
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