Energy-impact-resistant heating substrate for thermal printing and preparation method thereof

Abstract

The invention relates to the technical field of thermal printing head manufacturing, in particular to an energy-impact-resistant heating substrate for a thermal printing head and a preparation method of the energy-impact-resistant heating substrate, and the energy-impact-resistant heating substrate is high-temperature-resistant and capable of reducing adverse effects of thermal stress and is provided with an insulating substrate, a ground coat layer is arranged on the surface of the insulating substrate, and a heating resistor and an electrode wire are arranged on the ground coat layer. A protective layer covers the upper surfaces of the heating resistor body and part of the electrode lead, and the heating resistor body is characterized in that the heating resistor body is an energy-impact-resistant heating resistor body, the heating resistor body is made of a mixture of hafnium tantalum Hf / Ta alloy and SiC, the mass ratio of Hf to Ta in the hafnium tantalum alloy is (1-2): (8-9), the hafnium tantalum alloy accounts for 30-70% of the total mass of the heating resistor body, and the Hf / Ta alloy accounts for 30-70% of the total mass of the heating resistor body. The thickness of the heating resistor body is 10-500 nm, and the resistivity of the heating resistor body is 500-4000 E-8 omega.m.

Description

Technical field:

[0001] The invention relates to the technical field of thermal print head manufacturing, in particular to a heat generating substrate for a thermal print head which is resistant to high temperatures and can reduce the adverse effects of thermal stress and is resistant to energy shocks, and a preparation method thereof. Background technology:

[0002] The thermal print head is a component that prints using Joule heat. The temperature during printing is very high. In special circumstances, the printing area can reach over 1000°C. The existing thermal print heads are difficult to meet this requirement due to their high temperature resistance.

[0003] Existing high temperature resistant materials such as the invention of patent document CN102815971 disclose a Hf(Ta)C ultra-high temperature multiphase coating, which is composed of HfC and HfTaC2, wherein the mole fraction of HfTaC2 is 6-50%, and is evenly or gradiently distributed in the coating. Its preparation method is to place the surface-treated substrate in a low-pressure chemical vapor deposition furnace, with a mixed powder of hafnium tetrachloride and tantalum pentachloride as the hafnium source and tantalum source; methane as the carbon source; argon as the diluent gas; hydrogen as the reducing gas, and transport the mixed powder to the inside of the deposition furnace reactor, and deposit the Hf(Ta)C ultra-high temperature multiphase coating on the surface of the substrate material.

[0004] Patent document CN109320303 provides an ultra-high temperature oxidation-resistant and ablation-resistant coating and a preparation method thereof, which relates to the field of chemical vapor deposition technology. The present invention provides an ultra-high temperature oxidation-resistant and ablation-resistant coating, including a Ta / (Ta, Hf)C multi-layer multiphase composite coating formed by alternating superposition of a metal Ta coating and a (Ta, Hf)C multiphase coating. A method for preparing an ultra-high temperature oxidation-resistant and ablation-resistant coating is also provided, and the steps are as follows: S01, providing a pretreated substrate material; S02, preparing a (Ta, Hf)C multiphase coating on the surface of the substrate material, preparing a metal Ta transition coating on the surface of the (Ta, Hf)C multiphase coating, alternating deposition for multiple times, and finally ending the deposition with a (Ta, Hf)C multiphase coating to prepare a Ta / (Ta, Hf)C multi-layer multiphase composite coating. It is suitable for preparing ultra-high temperature protective coatings on the inner pore surfaces of substrates such as graphite and C / C composite materials, and improving the oxidation resistance, ablation resistance, and thermal shock resistance of the inner pore working surface of the substrate material.

[0005] Patent document CN109972120 relates to a method for preparing a multi-component composite carbide coating. It includes the following steps: (1) placing a mixed powder of TaCl5, HfCl4 and ZrCl4 in a crucible under an inert atmosphere; (2) placing a substrate sample on a support of a deposition furnace, introducing argon gas, and heating to a deposition temperature; (3) placing the crucible containing the mixed powder on a lifting support of a low temperature zone in a dual-temperature zone gasification furnace, connecting the crucible mouth with the high temperature zone, setting the heating temperatures of the low and high temperature zones, and heating to completely vaporize the mixed powder; (4) introducing H2 and CH4 into the deposition furnace, and introducing the completely vaporized mixed gas into the deposition furnace with a carrier gas, and depositing under normal pressure. This preparation method can obtain a multi-component composite coating with an accurate stoichiometric ratio of each component, and can ensure that the coating is tightly and firmly bonded to the substrate material and has excellent stability.

[0006] Patent document CN111072388B relates to a long-term ablation-resistant ultra-high melting point nitrogen-containing carbide ultra-high temperature ceramic and its application, providing a method of using ball milling + spark plasma sintering to prepare HfCx Ny ceramics with a density greater than or equal to 98% and a uniform C / N content distribution. The designed and prepared new ultra-high melting point ceramic overcomes the defects of existing ultra-high temperature ablation-resistant ceramics, such as too low ablation resistance temperature or too fast high temperature ablation loss; making it suitable for ultra-high temperature ablation protection of 3000℃ and above.

[0007] Although the high temperature resistant coating materials provided by the above prior art have high temperature resistant characteristics, they do not have electrical conductivity and cannot be directly applied to the production of thermal print heads. Summary of the invention:

[0008] In view of the shortcomings and deficiencies in the prior art, the present invention proposes a heat-generating substrate for a thermal print head that is resistant to high temperatures and can reduce the adverse effects of thermal stress and an energy shock resistance, and a preparation method thereof.

[0009] The present invention is achieved by the following measures:

[0010] A heating substrate for a thermal print head resistant to energy impact is provided, comprising an insulating substrate, a base glaze layer on the surface of the insulating substrate, a heating resistor and an electrode wire arranged on the base glaze layer, and a protective layer covering the upper surface of the heating resistor and part of the electrode wire. The heating resistor is characterized in that the heating resistor is an energy impact resistant heating resistor, the heating resistor is made of a mixture of a hafnium tantalum Hf / Ta alloy and SiC, the mass ratio of Hf to Ta in the hafnium tantalum alloy is 1-2:8-9, the hafnium tantalum alloy accounts for 30%-70% of the total mass of the heating resistor, the thickness of the heating resistor is 10-500nm, and the resistivity is 500-4000E-8Ω.m.

[0011] One end of the electrode wire of the present invention is connected to the heating resistor, and the other end is connected to the pad component, wherein the electrode wire includes an energy-resistant electrode wire segment and a common electrode wire segment, the energy-resistant electrode wire segment is located within 0.3 mm from the heating resistor, and the energy-resistant electrode wire segment is provided with a lower electrode wire and an upper electrode wire, the lower electrode wire is made of hafnium-rhenium Hf / Re alloy, and the upper electrode wire is made of hafnium-iridium Hf / Ir alloy, Hf in the lower electrode wire accounts for less than 10% of the total mass percentage, and the thickness is 0.1-2um, and Hf in the upper electrode wire accounts for less than 10% of the total mass percentage, and the thickness is 0.05-0.2um.

[0012] The bottom glaze layer in the present invention includes a bottom glaze heat storage layer located below and a HfO2 layer located above the bottom glaze heat storage layer. The bottom glaze heat storage layer is made of SiO2 as the main material and is prepared by a printing and sintering thick film process. The thickness is between several um and several hundred um, the thermal conductivity is 1±0.5W / mK, and the thermal expansion coefficient is 6.5±1e-6 / ℃. The HfO2 layer is made on the surface of the bottom glaze heat storage layer by PVD, CVD and other processes. The thickness is 0.1~10um. The melting point of HfO2 is 2758℃, which can improve the power resistance and temperature resistance of the print head. The thermal conductivity of the HfO2 layer is 1.6~2W / mK, and the thermal conductivity similar to that of the lower layer can maintain similar thermal response characteristics. The thermal expansion coefficient of HfO2 is 6±1e-6 / ℃. The similar thermal expansion coefficient can avoid interlayer peeling due to thermal expansion and contraction.

[0013] The protective layer of the present invention comprises an insulating protective layer, and the insulating protective layer is made of a mixture of HfO2 and SiN, or a mixture of HfO2 and SiON, or a mixture of HfO2 and SIALON.

[0014] The present invention also proposes a method for preparing the energy impact-resistant heating substrate for thermal printing as described above, wherein the heating resistor is prepared by the following steps:

[0015] Preparation method of Hf / Ta alloy & SIC in heating element,

[0016] Step 1: Prepare Hf / Ta alloy powder and SIC powder according to the mass ratio of Hf / Ta alloy: SIC = (3-7): (3-7), the purity of Hf / Ta alloy and SIC are both greater than or equal to 99.9%, and refine the prepared Hf / Ta alloy powder and SIC powder by ball milling and mix them evenly. After mixing evenly, the powder is filtered to obtain a powder with a particle size of less than 5 μm;

[0017] Step 2: Plasma sintering of the obtained mixed powder. The conditions of plasma sintering are: the temperature in the sintering furnace is 2000-2500°C, the temperature is kept for 15-20 minutes, the pressure is 35-50MPa, and the vacuum degree is less than 2Pa;

[0018] Step 3: The sintered material is cut into required sizes and welded to the target base to make a PVD target;

[0019] Step 4: Perform PVD magnetron sputtering in direct current (DC) mode or radio frequency (RF) mode, place the substrate with the base glaze into the cavity, set the vacuum degree in the cavity to below 1×10-4Pa, heat the cavity to 150-300°C, introduce argon gas, and use the pressure of 0.1-5Pa to prepare the heating resistor film layer using magnetron sputtering technology.

[0020] In step 4 of the present invention, since the material is conductive, a DC magnetron sputtering film-forming method is selected. In order to improve the density and adhesion of the material, a DC pulse method is further adopted on the basis of the DC mode. The DC pulse frequency is 50-150k, the pulse power density is 4-7w / cm2, the duty cycle is 20-45%, and the air pressure is 0.2-0.8Pa.

[0021] In the present invention, the HfO2 layer in the base glaze layer and the energy impact-resistant electrode wire segment (Hf+Re alloy, Hf+Ir alloy) in the electrode wire are prepared by directly sputtering the corresponding target materials.

[0022] The present invention can significantly improve the high temperature resistance of the heating resistor component of the thermal print head by providing an energy impact resistant heating resistor, while having conductive properties. In addition, by providing an energy impact resistant electrode wire segment in the electrode wire and correspondingly providing a base glaze layer and a protective layer with a new structure, the energy impact resistance and thermal stress resistance of the entire heating zone are further improved, thereby improving product quality. Description of the drawings:

[0023] Attached Figure 1 It is a cross-sectional view of a heating substrate for a thermal print head in the present invention.

[0024] Attached Figure 2 It is a schematic diagram of the local structure of the electrode wire in the present invention.

[0025] Attached Figure 3 It is a cross-sectional view of the heating resistor region of the heating substrate for the thermal print head of the present invention.

[0026] Figure numerals: insulating substrate 1, base glaze layer 2, base glaze heat storage layer 2-1, HfO2 layer 2-2, heating resistor 3, electrode wire 4, lower electrode wire 4-1, upper electrode wire 4-2, individual electrode 4b, common electrode 4a, protective layer 5. Specific implementation method:

[0027] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0028] Example:

[0029] This example provides a high energy resistant heat sensitive printing head heating substrate, as shown in the attached Figure 1 , 3 As shown, the heating substrate includes an insulating substrate 1, a base glaze layer 2, a heating resistor 3, individual electrodes 4b, a common electrode 4a, and a protective layer 5. A wear-resistant protective layer can be added to the protective layer 5 as needed. In this example, the base glaze layer 2 adopts a composite structure of a base glaze heat storage layer with SiO2 as the main material and a HfO2 layer; the heating resistor 3 is composed of a mixture of Hf / Ta alloy and SIC, and the components include at least two kinds of conductive materials and insulating materials. The resistivity can be adjusted by proportion to meet the product requirements of thermal print heads; some electrode layers adopt a double-layer structure, the lower electrode line 4-1 is composed of Hf+Re alloy, and the upper electrode line 4-2 is composed of Hf+Ir alloy; the insulating protective film in the protective layer is composed of at least one of a HfO2&SiN mixture or a HfO2&SiON mixture or a HfO2&SIALON mixture.

[0030] In this example, the bottom layer of the bottom glaze layer adopts a bottom glaze heat storage layer 2-1 with SiO2 as the main material. The bottom glaze heat storage layer 2-1 with SiO2 as the main material adopts a mixture of compounds composed of traditional bottom glaze materials such as Si, O, B, Zr, Ca, Al and other elements, and is prepared by printing and sintering thick film technology, with a thickness of several um to several hundred um; the thermal conductivity of the bottom glaze heat storage layer 2-1 is about 1W / mK, and the thermal expansion coefficient is 6.5±1e-6 / ℃. The HfO2 layer 2-2 is made by PVD, CVD and other processes with a thickness of 0.1 to 10 um. The melting point of the HfO2 layer 2-2 is 2758°C, which can improve the power resistance and temperature resistance of the print head. The thermal conductivity of the HfO2 layer 2-2 is 1.6 to 2 W / mK, which is similar to the thermal conductivity of the lower glaze heat storage layer 2-1 and can maintain similar thermal response characteristics. The thermal expansion coefficient of HfO2 is 6±1e-6 / °C. Similar thermal expansion coefficients can avoid interlayer peeling due to thermal expansion and contraction.

[0031] In this example, the heating resistor 3 can have a good bonding force with the base glaze layer and the protective layer. The selected heating resistor layer is composed of a mixture of Hf / Ta alloy and SiC. The ratio of Hf to Ta is 1-2:8-9. The ratio of Hf / Ta alloy is between 30% and 70%, the thickness is 10-500nm, and the resistivity of the mixture is 500-4000E-8Ω.m. The selected heating resistor layer is made by PVD or CVD processes; the thermal expansion coefficient of Hf is 5.8±1e-6 / ℃, and the thermal expansion coefficient of SIC is 4±1e-6 / ℃, which are relatively close, and the same as the lower layer of HfO2 Layer 2-2 is also relatively similar, while the thermal expansion coefficients of traditional heating element materials Ta and SiO2 are 15.8±1e-6 / ℃ and 6.5±1e-6 / ℃ respectively, which are quite different, and are also quite different from the HfO2 layer 2-2 below. Experiments have shown that the addition of Hf can reduce the difference in thermal expansion coefficients of the upper and lower layers to a certain extent, reducing thermal stress; the resistivity of Hf in the heating resistor layer is 29.6±2e-8Ω·m, SIC insulation, and the two can obtain different square resistances by adjusting different proportions to meet different resistance requirements, which is different from the traditional heating element material Ta (resistivity is 15±

[0032] 1e-8Ω·m) and SiO2 (insulation) are also relatively close and can be used as substitutes.

[0033] In this example, the resistance pattern of the heating resistor can be realized by a variety of process methods. Method 1: sputtering a mixture of Hf / Ta alloy and SiC as the resistance layer, using photolithography process, photoresist as a protective layer, and dry etching to form the resistance layer pattern. Commonly used etching gases include Ar, CF4, CHF3, O2, etc.

[0034] In this example, the electrode layer adopts a double-layer structure. Specifically, some electrode wires are energy-impact resistant electrode wires, including a lower electrode wire: composed of Hf+Re alloy, with an Hf ratio of less than 10% and a thickness of 0.1-2um, and an upper electrode wire: composed of Hf+Ir alloy, with an Hf ratio of less than 10% and a thickness of 0.05-0.2um. The selected electrode layer is made of PVD or CVD processes. The melting points of Hf+Re in the lower electrode wire are 2227°C and 3180°C, respectively, which are much higher than the Al with a melting point of about 600°C that is commonly used now. The thermal expansion coefficients of Hf+Re are 5.8±1e-6 / °C and 6.7±1e-6 / °C, which are less than 23±1e-6 / °C of Al, and are similar to the expansion coefficient of the heating element in the lower layer. In addition, the Re metal has good plasticity and toughness to ensure that it will not break at high temperatures. The resistivity of Hf+Re is 35.7e-8Ω·m and 5.42e-8Ω·m respectively, which is greater than 2.83e-8Ω·m of Al, so it is limited to use near heating elements with higher temperature requirements. Specifically, the electrode wire segment resistant to high energy impact in this example is only distributed in the area 0.3mm away from the heating resistor, and the proportion of Hf cannot be too high;

[0035] In order to obtain better anti-oxidation performance, a thin Hf+Ir alloy conductive layer with a thickness of 0.05~0.2um is made on the lower electrode line Hf+Re alloy. Ir has excellent anti-oxidation performance and can resist oxidation up to 2100℃. The thermal expansion coefficient of Ir is 6.4±1e-6 / ℃, which is similar to the lower electrode 1, and the resistivity is 4.7e-8Ω·m, which is also similar to the lower electrode 1.

[0036] The electrode layer described in this example can be realized by a variety of process methods. Method 1 is to sputter the electrode layer of Hf+Re alloy and Hf+Ir alloy, adopt photolithography process, use photoresist as a protective layer, and wet etching to form the electrode layer pattern. Various acid liquids are used as wet chemicals. Method 2 is to adopt photolithography process, use photoresist to protect unnecessary images, sputter the electrode layer of Hf+Re alloy and Hf+Ir alloy, remove the photoresist and the electrode layer above, and leave the pattern outside the photoresist to form the electrode layer pattern.

[0037] In this example, the insulating protective film in the protective layer is composed of at least one of a HfO2&SiN mixture, a HfO2&SiON mixture, or a HfO2&SIALON mixture, with a proportion of HfO2 below 20% and a total thickness between 1 and 20um. SiN is electrically insulating, with a temperature resistance of about 1900°C and a thermal expansion coefficient of 2.35±1e-6 / °C; SIALON is electrically insulating, with a melting point greater than 1500°C, a heat shock resistance greater than 900°C, and a thermal expansion coefficient of 2.6±1e-6 / °C. They are all relatively excellent temperature-resistant materials, and their expansion coefficients are close to those of the HfO2 of the lower glaze 2 and the Hf / Ta alloy of the heating element.

[0038] The insulating protective film adopts the Lift-Off process, and the bentonite powder is configured into a special slurry. The electrode pattern that needs to be exposed is covered by the printing process, and the insulating protective film HfO2&SiN mixture or HfO2&SiON mixture or HfO2&SIALON mixture is sputtered. Finally, the bentonite and the insulating protective film on top are removed to form the insulating protective film pattern. From the heat storage layer to the heating element, to the electrode, and then to the protective layer, the Hf element runs through it all the way, which can maintain the fusion between the layers.

[0039] This example further provides a method for preparing the heating resistor as described above, comprising the following steps:

[0040] S1: Hf / Ta alloy powder and SIC powder are prepared in a mass ratio of Hf / Ta alloy:SIC=6:4. The specific ratio is adjusted according to the resistance value of the print head to be made. The purity of Hf / Ta alloy and SIC are both greater than or equal to 99.9%. The prepared Hf / Ta alloy powder and SIC powder are refined by ball milling and mixed evenly. The mixed powder is filtered to obtain a powder with a particle size of less than 5um;

[0041] S2: The obtained mixed powder is subjected to plasma sintering. The conditions for plasma sintering are: the temperature in the sintering furnace is 2000-2500℃. The plasma sintering temperature does not necessarily need to reach the melting point of the sintered material. Spark plasma sintering (SPS) allows the powder particles to be quickly densified at a temperature below the melting point. Keep warm for 15-20 minutes, the pressure is 35-50MPa, and the vacuum degree is less than 2Pa;

[0042] S3: The sintered material is cut into required sizes and welded to the target base to make a PVD target.

[0043] S4: PVD magnetron sputtering process, the specific steps are: direct current (DC) or radio frequency (RF) can be used. Due to the conductivity of the material, the DC method is preferred, and the sputtering efficiency is higher. The substrate with the base glaze is placed in the cavity, and the vacuum degree in the cavity is set to below 1×10-4Pa. The cavity temperature is heated to 150-300°C, and argon gas is introduced with a pressure of 0.1-5Pa. The film layer is prepared using magnetron sputtering technology. In order to improve the density and adhesion of the material, a DC pulse method can be further used on the basis of the DC mode. The conditions are a frequency of 50-150k, a pulse power density of 4-7w / cm2, a duty cycle of 20-45%, and an air pressure of 0.2-0.8Pa.

[0044] The preparation method of the HfO2 layer and the electrode (Hf+Re alloy, Hf+Ir alloy) in the base glaze layer refers to the method of the heating element. The HfO2 layer and the electrode are directly sputtered by corresponding target materials. The electrode is a conductive material and can be prepared by DC or RF magnetron sputtering process. The HfO2 layer is a non-conductive material and is prepared by RF magnetron sputtering process.

[0045] The preparation method of protective film (HfO2&SiN or HfO2&SiON or HfO2&SIALON) etc. refers to the method of heating element. The target material can be a single target, which is made by mixed plasma sintering, or two independent double targets. When two independent targets are sputtered, they can be sputtered once in the same cavity according to different proportions. Because the target material is not conductive, the protective film is made by RF magnetron sputtering process.

[0046] The present invention can significantly improve the high temperature resistance of the heating resistor component of the thermal print head by providing an energy impact resistant heating resistor, while having conductive properties. In addition, by providing an energy impact resistant electrode wire segment in the electrode wire and correspondingly providing a base glaze layer and a protective layer with a new structure, the energy impact resistance and thermal stress resistance of the entire heating zone are further improved, thereby improving product quality.

Claims

1. A heating substrate for a thermal print head resistant to energy impact, comprising an insulating substrate, a base glaze layer on the surface of the insulating substrate, a heating resistor and an electrode wire arranged on the base glaze layer, and a protective layer covering the upper surface of the heating resistor and part of the electrode wire, characterized in that: The heating resistor is an energy impact-resistant heating resistor, which is made of a mixture of hafnium tantalum Hf / Ta alloy and SiC. The mass ratio of Hf and Ta in the hafnium tantalum alloy is 1-2:8-9, and the hafnium tantalum alloy accounts for 30% to 70% of the total mass of the heating resistor. The thickness of the heating resistor is 10 to 500 nm, and the resistivity is 500 to 4000E-8Ω.m.

2. The heat generating substrate for a thermal print head resistant to energy shock according to claim 1, characterized in that: One end of the electrode wire is connected to the heating resistor, and the other end is connected to the pad component, wherein the electrode wire includes an energy-resistant electrode wire segment and a common electrode wire segment, the energy-resistant electrode wire segment is located within 0.3 mm from the heating resistor, and the energy-resistant electrode wire segment is provided with a lower electrode wire and an upper electrode wire, the lower electrode wire is made of hafnium-rhenium Hf / Re alloy, and the upper electrode wire is made of hafnium-iridium Hf / Ir alloy, Hf in the lower electrode wire accounts for less than 10% of the total mass percentage, and the thickness is 0.1-2um, and Hf in the upper electrode wire accounts for less than 10% of the total mass percentage, and the thickness is 0.05-0.2um.

3. The heat generating substrate for a thermal print head resistant to energy shock according to claim 1, characterized in that: The bottom glaze layer includes a bottom glaze heat storage layer located below and a HfO2 layer located above the bottom glaze heat storage layer. The bottom glaze heat storage layer is mainly made of SiO2 and is prepared by a printing and sintering thick film process. The thickness is between several um and several hundred um, the thermal conductivity is 1±0.5W / mK, and the thermal expansion coefficient is 6.5±1e-6 / ℃. The HfO2 layer is made on the surface of the bottom glaze heat storage layer by PVD, CVD and other processes. The thickness is 0.1~10um. The melting point of HfO2 is 2758℃, which can improve the power resistance and temperature resistance of the print head. The thermal conductivity of the HfO2 layer is 1.6~2W / mK, and the thermal conductivity similar to that of the lower layer can maintain similar thermal response characteristics. The thermal expansion coefficient of HfO2 is 6±1e-6 / ℃. The similar thermal expansion coefficient can avoid interlayer peeling due to thermal expansion and contraction.

4. The heat generating substrate for a thermal print head resistant to energy shock according to claim 1, characterized in that: The protective layer includes an insulating protective layer, and the insulating protective layer is made of a mixture of HfO2 and SiN, or a mixture of HfO2 and SiON, or a mixture of HfO2 and SIALON.

5. A method for preparing a heat-generating substrate for thermal printing resistant to energy shock according to any one of claims 1 to 4, characterized in that: The heating resistor is prepared by the following steps: Preparation method of Hf / Ta alloy & SIC in heating element, Step 1: Prepare Hf / Ta alloy powder and SIC powder according to the mass ratio of Hf / Ta alloy: SIC = (3-7): (3-7), wherein the purity of Hf / Ta alloy and SIC is greater than or equal to 99.9%, and the prepared Hf / Ta alloy powder and SIC powder are refined by ball milling and mixed evenly, and the mixed powder is filtered to obtain a powder with a particle size of less than 5 μm; Step 2: Plasma sintering of the obtained mixed powder. The conditions of plasma sintering are: the temperature in the sintering furnace is 2000-2500°C, the temperature is kept for 15-20 minutes, the pressure is 35-50MPa, and the vacuum degree is less than 2Pa; Step 3: The sintered material is cut into required sizes and welded to the target base to make a PVD target; Step 4: Perform PVD magnetron sputtering in direct current (DC) mode or radio frequency (RF) mode. Place the substrate with the base glaze into the cavity, set the vacuum degree in the cavity to below 1×10-4Pa, heat the cavity to 150-300°C, introduce argon gas with a pressure of 0.1-5Pa, and use magnetron sputtering technology to prepare the heating resistor film layer.

6. The method for preparing a heat-generating substrate for thermal printing resistant to energy shock according to claim 5, characterized in that: In step 4, since the material is conductive, the DC magnetron sputtering film forming method is selected. In order to improve the density and adhesion of the material, a DC pulse method is further adopted on the basis of the DC mode. The DC pulse frequency is 50-150k, the pulse power density is 4-7w / cm2, the duty cycle is 20-45%, and the air pressure is 0.2-0.8Pa.

7. A method for manufacturing a heating substrate for a thermal print head according to any one of claims 1 to 5, characterized in that: The heating element resistance layer resistant to high energy impact adopts photolithography technology, uses photoresist as a protective layer, and forms the resistance layer pattern by dry etching, and the etching gas is selected from Ar, CF4, CHF3, and O2.

8. The method for preparing a heat-generating substrate for thermal printing resistant to energy shock according to claim 5, characterized in that: The HfO2 layer in the bottom glaze layer and the electrode wire segment resistant to energy impact in the electrode wire are prepared by directly sputtering the corresponding target materials.

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