CN115058686B - Preparation method for regulating and controlling growth orientation of Pt film crystal - Google Patents

Preparation method for regulating and controlling growth orientation of Pt film crystal Download PDF

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CN115058686B
CN115058686B CN202210695225.8A CN202210695225A CN115058686B CN 115058686 B CN115058686 B CN 115058686B CN 202210695225 A CN202210695225 A CN 202210695225A CN 115058686 B CN115058686 B CN 115058686B
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substrate
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film
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CN115058686A (en
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杨曌
丁燕
陆忠成
罗俊尧
李保昌
沓世我
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Guangdong Fenghua Advanced Tech Holding Co Ltd
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • 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
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    • 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
    • C23C14/34—Sputtering
    • C23C14/3457—Sputtering using other particles than noble gas ions
    • 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
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • 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 technical field of temperature sensing materials, and relates to a preparation method for regulating and controlling the growth orientation of Pt film crystals. The preparation method of the invention comprises the following process steps: patterning a mask, sputtering and coating, removing the mask and annealing. The buffer layer Ta layer and the functional layer Pt layer are sequentially deposited through the combination of a sputtering coating process and an annealing treatment process, and the adjustment and control of the crystal orientation of the Pt film layer are realized through adjusting and controlling the oxygen content in the sputtering process, the annealing treatment temperature and the heat preservation time. The Pt film layer obtained by the method has the advantages of various crystal orientations, high compactness, high TCR and good linearity, and the method has the characteristics of low cost, easiness in operation, easiness in realization of batch or large-scale production, high yield, high stability, excellent performance of the obtained film and the like, and has a positive effect of promoting the development of a Pt temperature sensor.

Description

Preparation method for regulating and controlling growth orientation of Pt film crystal
Technical Field
The invention belongs to the technical field of temperature sensing materials, and particularly relates to a preparation method for regulating and controlling the growth orientation of Pt film crystals.
Background
The temperature sensitive elements nowadays are developed towards high precision, miniaturization and high reliability. Pt is often used as a high-precision temperature sensing material due to its stable chemical and thermal properties. According to crystal growth dynamics, the atomic surface density of the Pt (111) surface is maximum, the surface energy is correspondingly minimum, the Pt film layer (less than or equal to 1 μm) prepared by the film deposition technology preferentially grows along the (111) crystal face, and other surfaces gradually disappear, so that the crystal orientation of the film layer is single, and the Temperature Coefficient of Resistance (TCR) performance of the film layer is reduced; in addition, the deposition rate is high in the sputtering process, the film layer is not completely formed inside, and a large number of defects such as vacancies and dislocation exist in the film layer structure inevitably, so that the film layer has poor compactness. Based on this, in order to obtain a film layer with various crystal orientations and good compactness, a method capable of regulating and controlling the growth process of the Pt film layer is necessary to be found, and the Pt temperature sensor is promoted to develop towards high precision, miniaturization and high reliability.
Disclosure of Invention
Aiming at the problems of single crystal orientation and non-compact film layer of the Pt film layer caused by the film deposition technology, the invention aims to provide a preparation method for regulating and controlling the crystal growth orientation of the Pt film layer, and the problems of single crystal orientation and non-compact film layer generated in the preparation process of the Pt film layer by the film deposition technology are effectively solved by combining a sputtering coating process with a post-treatment process.
In order to achieve the above purpose, the method specifically comprises the following technical scheme:
the invention aims to regulate and control the growth orientation of Pt film crystals by innovating sputtering coating and annealing treatment processes, and obtain the Pt film with few defects, compact film and excellent performance. The process flow of the Pt film preparation method comprises the following steps: patterning a mask, sputtering and coating, removing the mask and annealing.
A preparation method for regulating and controlling the growth orientation of Pt film crystals comprises the following process steps:
(1) Patterning the mask: sequentially carrying out spin coating, pre-baking, exposure, post-baking and development treatment on the clean substrate;
(2) Sputtering coating: sequentially depositing a Ta layer and a Pt layer on the substrate after the mask is patterned in the step (1) in a sputtering coating mode; the sputtering coating process parameters of the Pt layer are as follows: the sputtering atmosphere is an atmosphere containing 0-10% of oxygen and 90-100% of argon, the sputtering air pressure is 0.3-0.4 Pa, the sputtering power is 50-100W, and the sputtering time is 65-130 min; the sputtering coating process parameters of the Ta layer are as follows: the sputtering atmosphere is argon, the sputtering air pressure is 0.3-0.4 Pa, the sputtering power is 50-100W, and the sputtering time is 1-5min;
(3) Removing the mask: placing the substrate subjected to the sputtering coating in the step (2) in a photoresist removing solution to remove a mask;
(4) Annealing: and (3) annealing the substrate after the mask is removed in the step (3), and finally obtaining the substrate containing the Pt film layer.
According to the preparation method for regulating and controlling the growth orientation of the Pt film layer crystal, the Pt crystal orientation is successfully regulated and controlled, the Pt film layer crystal is changed from a single orientation into a plurality of orientations and coexists, the TCR and the linearity are improved, meanwhile, the defects in the film layer are reduced, and the film layer has better compactness.
The patterning mask is used for covering a specific area on the substrate by the colloid, and providing necessary preconditions for forming specific test pattern units on the substrate and the film layer thereof, so that subsequent testing and characterization are facilitated.
Preferably, the substrate in the step (1) is a ceramic substrate.
Further preferably, the ceramic substrate includes any one of alumina and aluminum nitride.
The substrate is also subjected to polishing, ultrasonic cleaning and drying pretreatment so as to remove impurities on the surface of the substrate.
Preferably, in the step (2), the sputtering atmosphere when depositing the Pt layer is an atmosphere containing 5-10% oxygen and 90% -95% argon, the sputtering air pressure is 0.3Pa, the sputtering power is 75W, and the sputtering time is 130min; the sputtering pressure was 0.3Pa, the sputtering power was 75W, and the sputtering time was 2min when the Ta layer was deposited.
Further preferably, in the step (2), the background vacuum degree at the time of depositing the Pt layer is 6.0X10 -4 Pa, bias voltage of 0-100V, deposition thickness of 400-800 nm, pt target purity of 99.999%, and substrate deposition temperature of 0-500 ℃.
Still more preferably, in the step (2), the bias voltage at the time of depositing the Pt layer is 100V, and the substrate deposition temperature is 200 ℃.
Preferably, in the step (2), the background vacuum degree when the Ta layer is deposited is 6.0X10 -4 Pa, bias voltage of 0 to 1The sputtering rate is 10nm/min at 00V, the purity of the Ta target is 99.999%, and the deposition temperature of the substrate is room temperature.
The forming process of the Ta layer and the Pt layer is controlled by controlling the technological parameters of the sputtering coating.
Step (3) the mask removal step enables removal of the mask formed by the patterned mask in step (1).
Preferably, the photoresist removing solution in the step (3) is acetone, and the mask removing process is performed in an ultrasonic environment.
Preferably, in the step (4), the process parameters of the annealing treatment are as follows: the temperature rising rate is 2.5-5 ℃/min, the temperature is 500-1020 ℃, and the heat preservation time is 2-8 h.
Still further preferably, in the step (4), the process parameters of the annealing treatment are as follows: the temperature rising rate is 2.5 ℃/min, and the temperature is 500-900 ℃.
The Pt film layer-containing substrate prepared by the preparation method has the characteristics of various crystal orientations, high compactness, high TCR and good linearity.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, through the combination of sputtering coating and annealing treatment, a buffer layer Ta layer and a functional layer Pt layer are sequentially deposited, and the regulation and control of the crystal orientation of the Pt film layer are realized through regulating and controlling the oxygen content in the sputtering process, the annealing treatment temperature and the heat preservation time. The basic principle is as follows: oxygen and Pt introduced in the sputtering process can form a Pt compound, so that the preferential orientation growth of Pt is inhibited, the Pt compound is decomposed through the regulation and control of the temperature and time in the annealing process, meanwhile, the further growth of crystal grains can be promoted, the internal defects are reduced, the crystal orientation in the film layer is various, the film layer is more compact, and finally the Pt film layer with various orientations and better compactness is obtained.
(2) According to the preparation method, the TCR and linearity of the Pt film layer are regulated and controlled through regulation and control of the crystal orientation of the Pt film layer in the film forming process, so that the defect of poor TCR and linearity of the Pt film layer in the conventional film deposition technology is overcome.
(3) The Pt film layer obtained by the preparation method has the advantages of multiple crystal orientations, high compactness, high TCR and good linearity.
(4) The preparation method provided by the invention has the characteristics of low cost, easiness in operation, easiness in realization of batch or large-scale production, high yield, high stability, excellent performance of the obtained film and the like, and has a positive effect on promoting the development of Pt temperature sensors.
Drawings
FIG. 1 is a schematic view showing a Pt crystal film forming process of the Pt film layers prepared in examples 1 to 3.
FIG. 2 is an XRD pattern of the Pt film layers prepared in examples 1-3, wherein As-reduced-0% represents the XRD pattern of the Pt film layer prepared in comparative example 1; 500-2 h-0%, 500-2 h-5%, 500-2 h-10% respectively represent example 1 in which O is introduced 2 XRD pattern of Pt film layer prepared under the gas with the volume ratio of 0%, 5% and 10% of Ar; 900-2 h-0%, 900-2 h-5%, 900-2 h-10% respectively represent the introduction of O in example 2 2 XRD pattern of Pt film layer prepared under the gas with the volume ratio of 0%, 5% and 10% of Ar; 900-8 h-0%, 900-8 h-5%, 900-8 h-10% respectively represent example 3 wherein O is introduced 2 XRD pattern of Pt film layer prepared under the condition of 0%, 5% and 10% of Ar volume ratio.
FIG. 3 is an SEM image of a Pt film layer obtained in comparative example 1, wherein (a), (b) and (c) represent the introduction of O during sputter coating, respectively 2 SEM images of Pt film layer obtained with 0%, 5%, 10% by volume of Ar gas.
FIG. 4 is an SEM image of a Pt film layer obtained in example 1, wherein (e), (f) and (g) respectively represent the introduction of O during sputtering coating 2 SEM images of Pt film layer obtained with 0%, 5%, 10% by volume of Ar gas.
FIG. 5 is an SEM image of a Pt film layer obtained in example 2, wherein (h), (i) and (j) respectively represent the introduction of O during sputter coating 2 SEM images of Pt film layer obtained with 0%, 5%, 10% by volume of Ar gas.
FIG. 6 is an SEM image of a Pt film layer obtained in example 3, wherein (k), (l) and (m) respectively represent the sputtering film formation timeGo into O 2 SEM images of Pt film layer obtained with 0%, 5%, 10% by volume of Ar gas.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described by means of specific examples.
The invention aims to regulate and control the growth orientation of Pt film crystals by innovating sputtering coating and annealing treatment processes, and obtain the Pt film with few defects, compact film and excellent performance. The preparation method of the Pt film layer comprises the following steps: patterning a mask, sputtering and coating, removing the mask and annealing. The Pt crystal film forming process of the Pt film layer is shown in figure 1.
Example 1
1. Patterning mask
And (3) sequentially ultrasonically cleaning a polished aluminum oxide substrate (Ra=0.0254-0.0412 μm) by acetone, absolute ethyl alcohol and deionized water for 10min, and then putting the polished aluminum oxide substrate into a baking oven for baking to remove impurities on the surface of the substrate. The cleaned polished alumina substrate was spin coated with photoresist (available from su red electronics chemicals, model RJZ-304), pre-baked, exposed, post-baked, and developed to complete the patterned mask. Wherein the photoresist dosage is 2 ml/time; spin coating rotation speed is 2500rpm, spin coating time is 30s; pre-baking is to treat at 100 ℃ for 90s; the exposure is under mercury lamp with exposure dose of 6mJ/cm 2 The exposure time is 6s; post-baking is to treat at 100 ℃ for 90s; the temperature of development was 25℃and the time was 50s.
2. Sputtering coating
1) And (3) performing buffer layer Ta layer sputtering process treatment on the substrate with the patterned mask by using a magnetron sputtering coating machine. The specific parameters are as follows: ta transition layer prepared by using Ta target with purity of 99.999% and background vacuum degree of 6×10 -4 Pa, the sputtering temperature of the substrate is room temperature, the sputtering pressure is 0.3Pa, the sputtering power is 75W, the argon flow is 40sccm, the sputtering time is 2min, and the sputtering rate is 10nm/min.
2) Sputtering functional layer Pt layer (Pt target material with purity of 99.999%) on the sample after sputtering Ta layer, and its specific processThe parameters are as follows: the sputtering power is 50W (RF), the sputtering air pressure is 0.3Pa, the sputtering time is 130min, the substrate deposition temperature is 200 ℃, the bias voltage is 100V, and O is respectively introduced in the sputtering process 2 And the volume ratio of the gas to Ar is 0%, 5% and 10%.
3. Removing the mask
And (3) putting the sputtered sample into acetone, and removing the mask and a sputtered layer above the mask until the photoresist is observed to be completely removed under a microscope.
4. Post-treatment annealing treatment process
And (3) placing the sample with the mask removed in a tubular annealing furnace, and annealing for 2 hours at a high temperature of 500 ℃ at a heating rate of 2.5 ℃/min in an atmospheric environment.
Example 2
1. Patterning mask
And (3) sequentially ultrasonically cleaning a polished aluminum oxide substrate (Ra=0.0254-0.0412 μm) by acetone, absolute ethyl alcohol and deionized water for 10min, and then putting the polished aluminum oxide substrate into a baking oven for baking to remove impurities on the surface of the substrate. The cleaned polished alumina substrate was spin coated with photoresist (available from su red electronics chemicals, model RJZ-304), pre-baked, exposed, post-baked, and developed to complete the patterned mask. Wherein the photoresist dosage is 2 ml/time; spin coating rotation speed is 2500rpm, spin coating time is 30s; pre-baking is to treat at 100 ℃ for 90s; the exposure is under mercury lamp with exposure dose of 6mJ/cm 2 The exposure time is 6s; post-baking is to treat at 100 ℃ for 90s; the temperature of development was 25℃and the time was 50s.
2. Sputtering coating
1) And (3) performing buffer layer Ta layer sputtering process treatment on the substrate with the patterned mask by using a magnetron sputtering coating machine. The specific parameters are as follows: ta transition layer prepared by using Ta target with purity of 99.999% and background vacuum degree of 6×10 -4 Pa, the sputtering temperature of the substrate is room temperature, the sputtering pressure is 0.3Pa, the sputtering power is 75W, the argon flow is 40sccm, the sputtering time is 2min, and the sputtering rate is 10nm/min.
2) Starting the functional layer Pt layer (99.999% Pt target)Specific process parameters are as follows: the sputtering power is 50W (RF), the sputtering air pressure is 0.3Pa, the sputtering time is 130min, the substrate deposition temperature is 200 ℃, the bias voltage is 100V, and O is respectively introduced in the sputtering process 2 And the volume ratio of the gas to Ar is 0%, 5% and 10%.
3. Removing the mask
And (3) putting the sputtered sample into acetone, and removing the mask and a sputtered layer above the mask until the photoresist is observed to be completely removed under a microscope.
4. Post-treatment annealing treatment process
And (3) placing the sample with the mask removed in a tubular annealing furnace, and annealing for 2 hours at a high temperature of 900 ℃ at a heating rate of 2.5 ℃/min in an atmospheric environment.
Example 3
1. Patterning mask
And (3) sequentially ultrasonically cleaning a polished aluminum oxide substrate (Ra=0.0254-0.0412 μm) by acetone, absolute ethyl alcohol and deionized water for 10min, and then putting the polished aluminum oxide substrate into a baking oven for baking to remove impurities on the surface of the substrate. The cleaned polished alumina substrate was spin coated with photoresist (available from su red electronics chemicals, model RJZ-304), pre-baked, exposed, post-baked, and developed to complete the patterned mask. Wherein the photoresist dosage is 2 ml/time; spin coating rotation speed is 2500rpm, spin coating time is 30s; pre-baking is to treat at 100 ℃ for 90s; the exposure is under mercury lamp with exposure dose of 6mJ/cm 2 The exposure time is 6s; post-baking is to treat at 100 ℃ for 90s; the temperature of development was 25℃and the time was 50s.
2. Sputtering coating
1) And (3) performing buffer layer Ta layer sputtering process treatment on the substrate with the patterned mask by using a magnetron sputtering coating machine. The specific parameters are as follows: ta transition layer prepared by using Ta target with purity of 99.999% and background vacuum degree of 6×10 -4 Pa, the sputtering temperature of the substrate is room temperature, the sputtering pressure is 0.3Pa, the sputtering power is 75W, the argon flow is 40sccm, the sputtering time is 2min, and the sputtering rate is 10nm/min.
2) Starting the sample sputtered with the Ta layer to perform a functional layer Pt layerPt target with purity of 99.999%) is sputtered, the specific process parameters are as follows: the sputtering power is 50W (RF), the sputtering air pressure is 0.3Pa, the sputtering time is 130min, the substrate deposition temperature is 200 ℃, the bias voltage is 100V, and O is respectively introduced in the sputtering process 2 And the volume ratio of the gas to Ar is 0%, 5% and 10%.
3. Removing the mask
And (3) putting the sputtered sample into acetone, and removing the mask and a sputtered layer above the mask until the photoresist is observed to be completely removed under a microscope.
4. Post-treatment annealing treatment process
And (3) placing the sample with the mask removed in a tubular annealing furnace, and annealing for 8 hours at a high temperature of 900 ℃ at a heating rate of 2.5 ℃/min under the atmospheric environment.
Comparative example 1
1. Patterning mask
And (3) sequentially ultrasonically cleaning a polished aluminum oxide substrate (Ra=0.0254-0.0412 μm) by acetone, absolute ethyl alcohol and deionized water for 10min, and then putting the polished aluminum oxide substrate into a baking oven for baking to remove impurities on the surface of the substrate. The cleaned polished alumina substrate was spin coated with photoresist (available from su red electronics chemicals, model RJZ-304), pre-baked, exposed, post-baked, and developed to complete the patterned mask. Wherein the photoresist dosage is 2 ml/time; spin coating rotation speed is 2500rpm, spin coating time is 30s; pre-baking is to treat at 100 ℃ for 90s; the exposure is under mercury lamp with exposure dose of 6mJ/cm 2 The exposure time is 6s; post-baking is to treat at 100 ℃ for 90s; the temperature of development was 25℃and the time was 50s.
2. Sputtering coating
1) And (3) performing buffer layer Ta layer sputtering process treatment on the substrate with the patterned mask by using a magnetron sputtering coating machine. The specific parameters are as follows: ta transition layer prepared by using Ta target with purity of 99.999% and background vacuum degree of 6×10 -4 Pa, the sputtering temperature of the substrate is room temperature, the sputtering pressure is 0.3Pa, the sputtering power is 75W, the argon flow is 40sccm, the sputtering time is 2min, and the sputtering rate is 10nm/min.
2) Samples of sputtered Ta layerSputtering of a functional layer Pt layer (Pt target with purity of 99.999%) is started, and specific technological parameters are as follows: the sputtering power is 50W (RF), the sputtering air pressure is 0.3Pa, the sputtering time is 130min, the substrate deposition temperature is 200 ℃, the bias voltage is 100V, and O is respectively introduced in the sputtering process 2 And the volume ratio of the gas to Ar is 0%, 5% and 10%.
3. Removing the mask
And (3) putting the sputtered sample into acetone, and removing the mask and a sputtered layer above the mask until the photoresist is observed to be completely removed under a microscope.
The sample obtained in this example was not subjected to a post-treatment annealing process after mask removal.
XRD patterns of the Pt film layers obtained in examples 1 to 3 and comparative example 1 are shown in FIG. 2. According to XRD spectrum analysis, the preparation method successfully regulates and controls the crystal orientation of Pt in the film layer, and the crystal of the Pt film layer can be changed into a state with multiple orientations coexisting from a single orientation.
SEM images of Pt film layers obtained in examples 1 to 3 and comparative example 1 are shown in FIGS. 3 to 6, and it can be seen from (b), (f), (i), (l) that the film layers are shown in the following Table O 2 The Pt film layer prepared in the atmosphere with the Ar volume ratio of 5 percent has the advantages that the grain size of the film layer is continuously increased, more grains are contacted, the vacancy defects are fewer and fewer, and the film layer is more compact along with the increase of the annealing treatment temperature of the film layer and the extension of the annealing treatment time.
The TCR (alpha) is obtained by testing the resistance values of Pt film layers at different temperatures and adopting the following formula (1),
wherein Δr=r 1 -R 0 ，ΔT＝T 1 -T 0 ，R 0 Is T 0 Resistance at temperature, R 1 Is T 1 Resistance at temperature, and T 0 At 0 ℃, T 1 Is 100 ℃.
The linearity is also called nonlinear error, by testing the resistance values of Pt film layers at different temperatures, drawing an R-T graph by using an origin and fitting, and the maximum deviation (delta Rmax) of the fitting result and the actual result and the percentage of full-scale output (R) are the linearity.
The test results of TCR and linearity of the Pt film prepared in examples 1-3 are shown in table 1, and as the annealing temperature of the Pt film increases and the annealing time increases, the grain size of the film increases, the contact between grains increases, the vacancy defects decrease, the film becomes denser, and the TCR increases. Therefore, the TCR and linearity of the film can be regulated and controlled by regulating and controlling the oxygen content, the annealing treatment temperature and the annealing treatment time when the Pt film is subjected to sputter coating, and the defect that the Temperature Coefficient of Resistance (TCR) of the film is reduced due to single crystal orientation of the Pt film is overcome.
TABLE 1 test results of thickness TCR and linearity of Pt film layers prepared in examples 1-3
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The preparation method for regulating and controlling the growth orientation of the Pt film layer crystal is characterized by comprising the following process steps:
(1) Patterning the mask: sequentially carrying out spin coating, pre-baking, exposure, post-baking and development treatment on the clean substrate;
(2) Sputtering coating: sequentially depositing a Ta layer and a Pt layer on the substrate after the mask is patterned in the step (1) in a sputtering coating mode;
the sputtering coating process parameters of the Pt layer are as follows: the sputtering atmosphere is an atmosphere containing 5-10% of oxygen and 90-95% of argon, the sputtering air pressure is 0.3-0.4 Pa, the sputtering power is 50-100W, the sputtering time is 65-130 min, the substrate deposition temperature is 200 ℃, and the deposition thickness is 400-800 nm; the sputtering coating process parameters of the Ta layer are as follows: the sputtering atmosphere is argon, the sputtering air pressure is 0.3-0.4 Pa, the sputtering power is 50-100W, and the sputtering time is 1-5min;
(3) Removing the mask: placing the substrate subjected to the sputtering coating in the step (2) in a photoresist removing solution to remove a mask;
(4) Annealing: annealing the substrate after the mask is removed in the step (3), and finally obtaining the substrate containing the Pt film layer; the process parameters of the annealing treatment are as follows: the temperature rising rate is 2.5-5 ℃/min, the temperature is 500-1020 ℃, and the heat preservation time is 2-8 h.
2. The method according to claim 1, wherein in the step (2), the sputtering atmosphere for depositing the Pt layer is an atmosphere containing 5 to 10% of oxygen and 90 to 95% of argon, the sputtering pressure is 0.3Pa, the sputtering power is 75W, and the sputtering time is 130min; the sputtering pressure was 0.3Pa, the sputtering power was 75W, and the sputtering time was 2min when the Ta layer was deposited.
3. The method of claim 1, wherein in step (2), the background vacuum level at the time of depositing the Pt layer is 6.0X10 -4 Pa, bias voltage of 0-100V, and purity of Pt target material of 99.999%.
4. The method of claim 3, wherein in step (2), the bias voltage is 100V and the substrate deposition temperature is 200 ℃.
5. The method of claim 1, wherein in step (2), the background vacuum level at the time of depositing the Ta layer is 6.0X10 -4 Pa, bias voltage is 0-100V, sputtering rate is 10nm/min, purity of Ta target is 99.999%, and substrate deposition temperature is room temperature.
6. The method of claim 1, wherein in step (4), the annealing process parameters are as follows: the temperature rising rate is 2.5 ℃/min, and the temperature is 500-900 ℃.
7. The method according to any one of claims 1 to 5, wherein the substrate in step (1) is a ceramic substrate.
8. The method of claim 7, wherein the ceramic substrate comprises any one of aluminum oxide and aluminum nitride.
9. The method according to any one of claims 1 to 5, wherein the sputter coating in the step (2) is magnetron sputter coating; the photoresist removing solution in the step (3) is acetone.
10. The Pt-containing film substrate produced by the production method according to any one of claims 1 to 9.
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