CN105671491B - Using the method for evaporation coating controllable preparation multilevel Bi Sb Te tilt column arrays - Google Patents

Using the method for evaporation coating controllable preparation multilevel Bi Sb Te tilt column arrays Download PDF

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CN105671491B
CN105671491B CN201610233479.2A CN201610233479A CN105671491B CN 105671491 B CN105671491 B CN 105671491B CN 201610233479 A CN201610233479 A CN 201610233479A CN 105671491 B CN105671491 B CN 105671491B
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multilevel
vacuum
vacuum chamber
substrate
tilt column
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CN105671491A (en
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谭明
郝延明
蔡元学
秦月婷
谢宁
吴泽华
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Tianjin University of Science and Technology
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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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
    • C23C14/0623—Sulfides, selenides or tellurides
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    • C01P2006/32—Thermal properties
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Abstract

The present invention relates to a kind of method using evaporation coating controllable preparation multilevel Bi Sb Te tilt column arrays, key step are as follows：By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed into Bi under 8~10MPa pressure1.5Sb0.5Te3Block；By 0.1~0.2g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment；Stop after 2~5 min high pure nitrogens are filled with into vacuum chamber, then to vacuum chamber, vacuum in vacuum chamber is reached 2.0 × 10- 4~5.0 × 10- 4Pa；Heated for controlling temperature power supply is opened, after temperature rises to 250~350 DEG C of predetermined temperature, the nm/min of sedimentation rate 12~20, the h of sedimentation time 2~3 are set in PID controller；Open AC power, regulation output current 160~170 A；Start the deposition on substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array.Whole deposition process is simple, and cost is cheap, is easy to large-scale production, resulting multilevel Bi1.5Sb0.5Te3Post array tilt grows, and nano wire, pillar array structure are homogeneous, are effectively guaranteed being uniformly distributed for nanometer phase, application effect highly significant.

Description

Using the method for evaporation coating controllable preparation multilevel Bi-Sb-Te tilt column arrays
Technical field
The present invention relates to a kind of method that multilevel tilt column array is prepared using simple physical vapour deposition (PVD), especially relate to A kind of and method using evaporation coating controllable preparation multilevel Bi-Sb-Te tilt column arrays.
Background technology
At present, thermoelectric material is a kind of solid material that can be realized heat energy and mutually be changed with electric energy, has structure simpler Singly, without mechanical moving element, high reliability, noiseless, small volume, the advantages of environment protection such as rotation or movement, it is well suited for Prepare small-scale power generation and local refrigeration device.Bismuth telluride-base material is best room temperature thermoelectric material at present, their commercialization The thermoelectric figure factor of blockZTTypically 1.0 or so.Prove that special construction low-dimensional nanosizing is to realize with experiment according to theoretical The effective way that pyroelectric material performance is broken through, especially through the one-dimensional array to Fine Texture of Material, improve Fermi can near Density of electronic states and lift the Seebeck coefficients of bismuth telluride-base thermoelectric material；Increase the face body ratio of material and improve its surface State, it is beneficial to the electric transmission of this kind of topological insulator structure material, improves the conductance of material；Increase interface and improve phonon and dissipate Rate is penetrated, causes the thermal conductivity that material is greatly reduced.Therefore, the one-dimensional array of Fine Texture of Material is to realize bismuth telluride-based thermoelectric The important channel that material property is broken through, also provide a new think of to develop the new high efficiency thermoelectric micro element with special construction Road.
There are a variety of methods to prepare bismuth telluride-base material nano structure all the time, including electrochemical deposition, gas- The methods of liquid-solid catalytic growth, photoetching and anisotropic etching technology, these synthetic methods primary disadvantage is that their techniques too Complicated and condition is harsh, and reaction product is impure or needs removing template, is difficult in device application.Moreover these Method is hardly possible to be assembled into orderly multilevel post array and is based on nano wire, novel complicated multilevel structure shadow on a large scale The transmission of carrier and phonon in material is rung, so as to make material have excellent thermoelectricity capability.In work before us, The Sb of multilevel is successfully prepared using the physical vapour deposition (PVD) of simplicity2Te3Nano wire bundle array, any end-blocking is not used Agent or hard template, and this is still challenge, a kind of simply applicable method controllable preparation multilevel Bi of exploitation1.5Sb0.5Te3Incline Batter post array.Understood according to us, novel multilevel Bi1.5Sb0.5Te3Pillar array structure is to yet there are no report, more The multilevel Bi of growth is not tilted1.5Sb0.5Te3The patent and document report of pillar array structure.
Therefore it provides a kind of technique is simple, step is reasonable, significant effect using evaporation coating controllable preparation multilevel Bi1.5Sb0.5Te3The method of tilt column array, it is one of current problem anxious to be resolved of art personnel.
The content of the invention
It is an object of the present invention to overcome the above deficiencies, there is provided a kind of technique is simple, step is reasonable, significant effect Using the method for evaporation coating controllable preparation multilevel Bi-Sb-Te tilt column arrays.
The technical solution adopted in the present invention is to achieve the above object：One kind uses evaporation coating controllable preparation multilevel The method of Bi-Sb-Te tilt column arrays, it is characterised in that preparation process is as follows：
（1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is suppressed under the MPa pressure of 8MPa~10 Into Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
（2）Substrate takes out after being cleaned by ultrasonic 5min~10min respectively in acetone, absolute ethyl alcohol and deionized water, is used in combination High pure nitrogen（Mass percent purity 99.999%）Drying；
（3）By 0.1g~0.2g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, substrate Sample stage center is positioned over, adjusts the angle of sample stage and horizontal planeθ=5°~45°；Adjust the distance d of substrate center and tungsten boat The cm of=12 cm~18；
（4）The min high pure nitrogens of 2min~5 are filled with into vacuum chamber（Mass percent purity 99.999%）After stop, with Afterwards to vacuum chamber, vacuum in vacuum chamber is set to reach 2.0 × 10- 4Pa~5.0 × 10- 4Pa；
（5）Vacuum reaches 2.0 × 10- 4Pa~5.0 × 10- 4During Pa, heated for controlling temperature power supply is opened, sets heating-up temperature 250 DEG C~350 DEG C, start to heat up to substrate；
（6）After temperature rises to 250 DEG C~350 DEG C of predetermined temperature, the nm/min of sedimentation rate 12 is set in PID controller The h of~20 nm/min, the h of sedimentation time 2~3；
（7）Open AC power, the A of regulation output current 160 A~170；Start the deposition on substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array；
（8）Preparation is finished, and closes AC power, and after being cooled to 20 DEG C~40 DEG C with vacuum coating equipment, taking-up is made in base Deposition tilts the Bi of pillar array structure with multilevel on plate1.5Sb0.5Te3。
The beneficial effects of the invention are as follows：In order to solve multilevel Bi1.5Sb0.5Te3Tilt column array thermoelectric material is synthesizing Problems existing for aspect, by size, sample stage and the horizontal plane angle and substrate that adjust AC power output current Temperature, Bi is evaporated in vacuum chamber1.5Sb0.5Te3Raw material, directly deposit on the glass substrate with Bi1.5Sb0.5Te3Tilt column Array structure.Whole deposition process is simple, and cost is cheap, is easy to large-scale production, resulting multilevel Bi1.5Sb0.5Te3Post array tilt grows, and nano wire, pillar array structure are homogeneous, is effectively guaranteed uniformly dividing for nanometer phase Cloth.Performance test shows the Bi with multilevel array structure1.5Sb0.5Te3Excellent material performance, and tilt the multistage of growth The multilevel pillar array structure material property that secondary pillar array structure material property grows more vertically, which has, significantly to be lifted, therefore is introduced The multilevel pillar array structure for tilting growth is a kind of effective way for improving pyroelectric material performance.Utilize the vacuum evaporation of simplicity Coating method can process Bi on a large scale1.5Sb0.5Te3Multilevel tilt column array, method is novel, simple, production environment bar Part is loose, has the originality of technology, has the practical value of highly significant, device is processed into facilitate applied to industrialization, Great economic benefit can be createed.
Brief description of the drawings
Fig. 1 is multilevel Bi made from the embodiment of the present invention 11.5Sb0.5Te3The XRD of tilt column array；
Fig. 2 is multilevel Bi made from the embodiment of the present invention 11.5Sb0.5Te3The SEM of tilt column array surface；
Fig. 3 is multilevel Bi made from the embodiment of the present invention 11.5Sb0.5Te3The SEM of tilt column array side.
Fig. 4 is multilevel Bi made from the embodiment of the present invention 21.5Sb0.5Te3The XRD of tilt column array；
Fig. 5 is multilevel Bi made from the embodiment of the present invention 21.5Sb0.5Te3The SEM of tilt column array surface；
Fig. 6 is multilevel Bi made from the embodiment of the present invention 21.5Sb0.5Te3The SEM of tilt column array side.
Fig. 7 is multilevel Bi made from the embodiment of the present invention 31.5Sb0.5Te3The XRD of tilt column array；
Fig. 8 is multilevel Bi made from the embodiment of the present invention 31.5Sb0.5Te3The SEM of tilt column array surface；
Fig. 9 is multilevel Bi made from the embodiment of the present invention 31.5Sb0.5Te3The SEM of tilt column array side.
Figure 10 is multilevel Bi made from the embodiment of the present invention 41.5Sb0.5Te3The XRD of tilt column array；
Figure 11 is multilevel Bi made from the embodiment of the present invention 41.5Sb0.5Te3The SEM of tilt column array surface；
Figure 12 is multilevel Bi made from the embodiment of the present invention 41.5Sb0.5Te3The SEM of tilt column array side.
Embodiment
Below in conjunction with accompanying drawing and preferred embodiment, to according to embodiment provided by the invention, feature, details are as follows：
The present invention prepares multilevel Bi using vacuum evaporatation1.5Sb0.5Te3Tilt column array, include following system Standby step：
（1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed under 8~10 MPa pressure Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
（2）Substrate takes out after being cleaned by ultrasonic 5~10 min respectively in acetone, absolute ethyl alcohol and deionized water, and with height Pure nitrogen gas（Mass percent purity 99.999%）Drying；
（3）By 0.1~0.2g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, substrate Sample stage center is positioned over, adjusts the angle of sample stage and horizontal planeθ=5~45°；Adjust the distance d=of substrate center and tungsten boat 12~18 cm；
（4）2~5 min high pure nitrogens are filled with into vacuum chamber（Mass percent purity 99.999%）After stop, then it is right Vacuum chamber, vacuum in vacuum chamber is set to reach 2.0 × 10- 4~5.0 × 10- 4Pa；
（5）Vacuum reaches 2.0 × 10- 4~5.0 × 10- 4During Pa, heated for controlling temperature power supply is opened, sets heating-up temperature 250 ~350 DEG C, start to heat up to substrate；
（6）After temperature rises to 250~350 DEG C of predetermined temperature, the nm/ of sedimentation rate 12~20 is set in PID controller Min, the h of sedimentation time 2~3；
（7）Open AC power, regulation output current 160~170 A；Start the deposition on substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array；
（8）Preparation is finished, and closes AC power, and after being cooled to 20~40 DEG C with vacuum coating equipment, taking-up is made in substrate Upper deposition tilts the Bi of pillar array structure with multilevel1.5Sb0.5Te3。
Embodiment 1
Evaporation coating prepares multilevel Bi on the glass substrate1.5Sb0.5Te3Tilt column array；
（1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed under 8MPa pressure Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
（2）Glass substrate（Or glass plate）After being cleaned by ultrasonic 5min respectively in acetone, absolute ethyl alcohol and deionized water Take out, and use high pure nitrogen（Mass percent purity 99.999%）Drying；
（3）By 0.1g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, and glass substrate is put Sample stage center is placed in, adjusts the angle of sample stage and horizontal planeθ=5°；Adjust glass substrate center and the distance d=15 of tungsten boat cm；
（4）Stop after 3min high pure nitrogens are filled with into vacuum chamber, then to vacuum chamber, make vacuum house vacuum Degree reaches 2.0 × 10- 4Pa；
（5）Vacuum reaches 2.0 × 10- 4During Pa, heated for controlling temperature power supply is opened, 300 DEG C of heating-up temperature is set, starts pair Substrate heats up；
（6）After temperature rises to 300 DEG C of predetermined temperature, the nm/min of sedimentation rate 15 is set in PID controller, during deposition Between 2 h；
（7）Open AC power, regulation output current 165 A；Start deposition on the glass substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array；
（8）Preparation is finished, and closes AC power, and after being cooled to 25 DEG C with vacuum coating equipment, taking-up is made in glass substrate Upper deposition tilts the Bi of pillar array structure with multilevel1.5Sb0.5Te3。
Using X-ray diffractometer（Rigaku D/MAX 2200）To multilevel Bi made from embodiment 11.5Sb0.5Te3Incline Batter post array carries out material phase analysis, as shown in figure 1, multilevel Bi made from explanation1.5Sb0.5Te3Tilt column array is Bi1.5Sb0.5Te3Simple substance, and edge (0 1 5) crystal orientation preferential growth.
Using SEM（FE-SEM, Sirion 200）Multilevel made from lower observation embodiment 1 Bi1.5Sb0.5Te3Tilt column array, its surface topography such as Fig. 2, it is known that it is made up of nanometer or submicron order post array, can from section To find out, Bi1.5Sb0.5Te3Post array near vertical grows, and the nanowire diameter in post array is 20~50 nm, and line is by a lot Tiny nano dot or nano particle composition, line are then assembled into post, and stereoscan photograph is as shown in Figure 3.Bi1.5Sb0.5Te3Post array Structure is homogeneous, is effectively guaranteed being uniformly distributed for nanometer phase.
Embodiment 2
Evaporation coating prepares multilevel Bi on the glass substrate1.5Sb0.5Te3Tilt column array；
（1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed under 10MPa pressure Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
（2）Glass substrate（Or glass plate）After being cleaned by ultrasonic 8min respectively in acetone, absolute ethyl alcohol and deionized water Take out, and use high pure nitrogen（Mass percent purity 99.999%）Drying；
（3）By 0.1g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, and glass substrate is put Sample stage center is placed in, adjusts the angle of sample stage and horizontal planeθ=30°；Adjust glass substrate center and the distance d=of tungsten boat 15 cm；
（4）Stop after 5min high pure nitrogens are filled with into vacuum chamber, then to vacuum chamber, make vacuum house vacuum Degree reaches 2.0 × 10- 4Pa；
（5）Vacuum reaches 2.0 × 10- 4During Pa, heated for controlling temperature power supply is opened, 300 DEG C of heating-up temperature is set, starts pair Substrate heats up；
（6）After temperature rises to 300 DEG C of predetermined temperature, the nm/min of sedimentation rate 15 is set in PID controller, during deposition Between 2 h；
（7）Open AC power, regulation output current 165 A；Start deposition on the glass substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array；
（8）Preparation is finished, and closes AC power, and after being cooled to 25 DEG C with vacuum coating equipment, taking-up is made in glass substrate Upper deposition tilts the Bi of pillar array structure with multilevel1.5Sb0.5Te3。
Using X-ray diffractometer to multilevel Bi made from embodiment 21.5Sb0.5Te3Canted arrays carry out material phase analysis, As shown in figure 4, multilevel Bi made from explanation1.5Sb0.5Te3Tilt column array is Bi1.5Sb0.5Te3Simple substance, and it is brilliant along (0 1 5) To preferential growth.
Using multilevel Bi made from observation embodiment 2 under SEM1.5Sb0.5Te3Tilt column array, its table Face pattern such as Fig. 5, it is known that be made up of nanometer or submicron order post array, from section as can be seen that Bi1.5Sb0.5Te3Post array inclines Sideways growth, the nanowire diameter in post array are 20~50 nm, and line is made up of many tiny nano dots or nano particle, and line is again Post is assembled into, stereoscan photograph is as shown in Figure 6.Bi1.5Sb0.5Te3Pillar array structure is homogeneous, is effectively guaranteed nanometer phase It is uniformly distributed.
Embodiment 3
Evaporation coating prepares multilevel Bi on the glass substrate1.5Sb0.5Te3Tilt column array；
（1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed under 9MPa pressure Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
（2）Glass substrate（Or glass plate）After being cleaned by ultrasonic 8min respectively in acetone, absolute ethyl alcohol and deionized water Take out, and use high pure nitrogen（Mass percent purity 99.999%）Drying；
（3）By 0.1g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, and glass substrate is put Sample stage center is placed in, adjusts the angle of sample stage and horizontal planeθ=45°；Adjust glass substrate center and the distance d=of tungsten boat 15 cm；
（4）Stop after 3min high pure nitrogens are filled with into vacuum chamber, then to vacuum chamber, make vacuum house vacuum Degree reaches 2.5 × 10-4Pa；
（5）Vacuum reaches 2.5 × 10- 4During Pa, heated for controlling temperature power supply is opened, 300 DEG C of heating-up temperature is set, starts pair Substrate heats up；
（6）After temperature rises to 300 DEG C of predetermined temperature, the nm/min of sedimentation rate 15 is set in PID controller, during deposition Between 2 h；
（7）Open AC power, regulation output current 165 A；Start deposition on the glass substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array；
（8）Preparation is finished, and closes AC power, and after being cooled to 30 DEG C with vacuum coating equipment, taking-up is made in glass substrate Upper deposition tilts the Bi of pillar array structure with multilevel1.5Sb0.5Te3。
Above example 3 is the preferable citing of technical solution of the present invention.
Using X-ray diffractometer to multilevel Bi made from embodiment 31.5Sb0.5Te3Canted arrays carry out material phase analysis, As shown in fig. 7, multilevel Bi made from explanation1.5Sb0.5Te3Tilt column array is Bi1.5Sb0.5Te3Simple substance, and along (0 1 5) with (1 0 10) crystal orientation preferential growth.
Using multilevel Bi made from observation embodiment 3 under SEM1.5Sb0.5Te3Tilt column array, its table Face pattern such as Fig. 8, it is known that be made up of nanometer or submicron order post array, from section as can be seen that Bi1.5Sb0.5Te3Post array inclines Sideways growth, the nanowire diameter in post array are 20~50 nm, and line is made up of many tiny nano dots or nano particle, and line is again Post is assembled into, stereoscan photograph is as shown in Figure 9.Bi1.5Sb0.5Te3Pillar array structure is homogeneous, is effectively guaranteed nanometer phase It is uniformly distributed.
Embodiment 4
Evaporation coating prepares multilevel Bi on the glass substrate1.5Sb0.5Te3Tilt column array；
（1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed under 9MPa pressure Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
（2）Glass substrate（Or glass plate）After being cleaned by ultrasonic 10min respectively in acetone, absolute ethyl alcohol and deionized water Take out, and use high pure nitrogen（Mass percent purity 99.999%）Drying；
（3）By 0.2g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, and glass substrate is put Sample stage center is placed in, adjusts the angle of sample stage and horizontal planeθ=45°；Adjust glass substrate center and the distance d=of tungsten boat 18 cm；
（4）Stop after 3min high pure nitrogens are filled with into vacuum chamber, then to vacuum chamber, make vacuum house vacuum Degree reaches 2.5 × 10-4Pa；
（5）Vacuum reaches 2.5 × 10- 4During Pa, heated for controlling temperature power supply is opened, 350 DEG C of heating-up temperature is set, starts pair Substrate heats up；
（6）After temperature rises to 350 DEG C of predetermined temperature, the nm/min of sedimentation rate 18 is set in PID controller, during deposition Between 3 h；
（7）Open AC power, regulation output current 170 A；Start deposition on the glass substrate and prepare multilevel Bi1.5Sb0.5Te3Tilt column array；
（8）Preparation is finished, and closes AC power, and after being cooled to 30 DEG C with vacuum coating equipment, taking-up is made in glass substrate Upper deposition tilts the Bi of pillar array structure with multilevel1.5Sb0.5Te3。
Using X-ray diffractometer to multilevel Bi made from embodiment 41.5Sb0.5Te3Canted arrays carry out material phase analysis, As shown in Figure 10, multilevel Bi made from explanation1.5Sb0.5Te3Tilt column array is Bi1.5Sb0.5Te3Simple substance, and edge (0 1 5) Crystal orientation preferential growth.
Using multilevel Bi made from observation embodiment 4 under SEM1.5Sb0.5Te3Tilt column array, its table Face pattern such as Figure 11, it is known that be made up of nanometer or submicron particles, from section as can be seen that Bi1.5Sb0.5Te3Post array inclines Sideways growth, the column diameter in post array are 50~200 nm, and post is made up of many tiny nano dots or nano particle, ESEM Photo is as shown in figure 12.Bi1.5Sb0.5Te3Pillar array structure is homogeneous, is effectively guaranteed being uniformly distributed for nanometer phase.The present invention It is that multilevel is prepared using simple physical vapour deposition (PVD)（Point, line, the post of more sizes and various dimensions）Bi1.5Sb0.5Te3Tilt column Array approach, main feature are as follows：
（1）The novel multilevel Bi prepared using evaporation coating method1.5Sb0.5Te3Pillar array structure is tilted, is conveniently processed into Device, can be with other micro fabrication perfect adaptations.Utilize modern means of testing, system research multilevel tilt column array junctions Influence of the structure to material macroscopic view thermoelectricity capability, corresponding formation mechenism model, structure-performance relation are established, to develop and developing New heightZTNormal temperature area thermoelectric material and device provide new thinking.
（2）Performance test shows multilevel Bi1.5Sb0.5Te3Tilt column array performance is excellent, and with the more of inclination growth Level pillar array structure material property has compared with Common construction materials performance significantly to be lifted, therefore introduces the multilevel for tilting growth Pillar array structure is a kind of effective way for improving pyroelectric material performance.
（3）Bi can be processed on a large scale using the vacuum evaporatation of simplicity1.5Sb0.5Te3Multilevel tilt column Array, method is novel, simple, and production environment condition is loose, has the originality of technology, has significant practical value and economy to imitate Benefit.
The Bi of pillar array structure is tilted with multilevel1.5Sb0.5Te3Material properties test result（It is shown in Table 1）Compared to nearest On Bi1.5Sb0.5Te3Material literature reports result, such as：Y. the highest thermoelectric figure factor that Yu etc. obtains in temperature 442KZT max =0.78（Intermetallics, 66, 40-47, 2015）；Y. Pan etc. obtains in temperature 323KZT=0.96 （Materials Science and Engineering B, 197, 75-81, 2015）；D. Suh etc. is in temperature 330K AchieveZT=0.78（Nano Energy, 13, 67-76, 2015）, this shows that our multilevel tilts pillar array structure Bi1.5Sb0.5Te3Excellent material performance.This is due to the way that the array of highly directional crystal face, line and post builds a relative optimization Footpath is that carrier direction in face is transmitted；And the structural membrane has the phonon that multiple dimensioned crystal grain is responsible for scattering various wavelength, In face direction it include many gaps and highdensity rough interfaces, these, which produce thermal resistances, causes this novel post array to have low heat Lead；Multilevel array structure process is especially tilted induction of more useful change in interface, these are to cause to tilt to grow Multilevel pillar array structure material face in excellent performance basic reason, therefore introduce tilt growth multilevel post array junctions Structure is a kind of effective way for improving pyroelectric material performance.
Table 1 tilts the multilevel Bi of growth1.5Sb0.5Te3Columnar arrays are at room temperature（300K）Pyroelectricity in the face of test Can, each value is five test result average values.
It is above-mentioned that the method for using evaporation coating controllable preparation multilevel Bi-Sb-Te tilt column arrays is entered with reference to embodiment Capable detailed description, it is illustrative rather than limited, therefore change in the case where not departing from present general inventive concept and repaiies Change, should belong within protection scope of the present invention.

Claims (1)

  1. A kind of 1. method using evaporation coating controllable preparation multilevel Bi-Sb-Te tilt column arrays, it is characterised in that prepare step It is rapid as follows：
    （1）By the Bi that mass percent purity is 99.99%1.5Sb0.5Te3Powder is pressed under the MPa pressure of 8MPa~10 Bi1.5Sb0.5Te3Block；The Bi1.5Sb0.5Te3The average grain diameter of powder is less than 50 μm；
    （2）Substrate takes out after being cleaned by ultrasonic 5min~10min respectively in acetone, absolute ethyl alcohol and deionized water, and uses quality The high pure nitrogen of percent purity 99.999% dries up；
    （3）By 0.1g~0.2g Bi1.5Sb0.5Te3Block is put into the tungsten boat of the vacuum chamber of vacuum coating equipment, and substrate is placed In sample stage center, the angle of regulation sample stage and horizontal planeθ=5°~45°；Adjust the distance d=12 of substrate center and tungsten boat The cm of cm~18；
    （4）Stop after 2min~high pure nitrogen of 5 min mass percents purity 99.999% is filled with into vacuum chamber, then to true Empty room vacuumizes, and vacuum in vacuum chamber is reached 2.0 × 10- 4Pa~5.0 × 10- 4Pa；
    （5）Vacuum reaches 2.0 × 10- 4Pa~5.0 × 10- 4During Pa, heated for controlling temperature power supply is opened, sets heating-up temperature 250 DEG C~350 DEG C, start to heat up to substrate；
    （6）After temperature rises to 250 DEG C~350 DEG C of predetermined temperature, nm/min~20 of sedimentation rate 12 are set in PID controller The h of nm/min, the h of sedimentation time 2~3；
    （7）Open AC power, the A of regulation output current 160 A~170；Start the deposition on substrate and prepare more sizes and multidimensional Point, line, the post Bi of degree1.5Sb0.5Te3Tilt column array；
    （8）Preparation is finished, and closes AC power, and after being cooled to 20 DEG C~40 DEG C with vacuum coating equipment, taking-up is made on substrate Deposition tilts the Bi of pillar array structure with multilevel1.5Sb0.5Te3。
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