KR102156664B1 - Resistive oxide thin film for bolometer and method for manufacturing the same - Google Patents

Abstract

The oxide resistance thin film for a bolometer according to the present invention includes an oxide layer having a cubic spinel crystal structure provided on a substrate, and the oxide layer contains nickel, manganese and copper (Ni,Mn,Cu) ₃ O ₄ family parent; And a first additive, which is an element added to the parent body and maintains a valence state even when the temperature changes, and a second additive, which is an element whose valency changes according to temperature change.

Description

Oxide resistance thin film for bolometer and method for manufacturing the same {Resistive oxide thin film for bolometer and method for manufacturing the same}

The present invention relates to an oxide resistance thin film for a bolometer and a method of manufacturing the same, and more particularly, to an oxide resistance thin film for a bolometer having a high resistance temperature coefficient and a low specific resistance, and a method of manufacturing the same.

The temperature coefficient of resistance (TCR) of the bolometer thin film used as a sensing material in a bolometer, an infrared sensor that detects changes in infrared, using a thin film for sensing materials whose resistance changes according to temperature changes due to absorption of infrared rays. The performance of the bolometer is determined by the specific resistance and the fluctuation of the resistance in the low frequency band (1/f noise), and the higher the absolute value of the resistance temperature coefficient, which is the rate at which the resistance changes with temperature change, the better the performance of the bolometer. have. In addition, the bolometer thin film, which affects the sensitivity of the bolometer, can be used as an excellent sensing material as the resistance temperature coefficient is large and the specific resistance and 1/f noise are small.

In addition, the bolometer thin film should be manufactured at low cost by maintaining compatibility with the complementary metal oxide semiconductor (CMOS) process for manufacturing a read integrated circuit (ROIC), and the problem of bubbling of the sacrificial layer of organic matter and ROIC during the bolometer manufacturing process. In order not to damage the circuit, the heat treatment temperature of about 400℃ or less must be satisfied.

Infrared sensors used in vehicle night vision or advanced driver assistance systems (Advanced Driver Assistance Systems, ADAS) are exposed to a high temperature environment either environmentally or by heating the device, so the application requires high sensitivity even at high temperatures other than room temperature. Increasingly, an infrared sensor having a high resistance temperature coefficient in a temperature range of various environments is required.

However, vanadium oxide (VO _x ), a material commonly used in bolometer thin films, has a resistance temperature coefficient of about -2%/K at room temperature, while a resistance temperature coefficient lower than about -1%/K at high temperature, It is difficult to obtain reproducibility because it is difficult to obtain reproducibility as it undergoes a state change from an insulator or semiconductor at a specific temperature. In addition, for stable thin film deposition, it is a problem that it must be manufactured at a high temperature of 500℃ or higher with expensive special equipment such as a sputtering device. Have them.

Therefore, there is a need for an oxide resistance thin film for a bolometer capable of manufacturing a bolometer thin film having a high resistance temperature coefficient at a high temperature as well as room temperature and a low specific resistance at a low heat treatment temperature.

US 6489613 B

The present invention provides an oxide resistance thin film for a bolometer that can have a high resistance temperature coefficient and low specific resistance at a low heat treatment temperature as well as at room temperature and at a high temperature, and a method of manufacturing the same.

The oxide resistance thin film for a bolometer according to an embodiment of the present invention includes an oxide layer having a cubic spinel crystal structure provided on a substrate, and the oxide layer contains nickel, manganese, and copper (Ni,Mn ,Cu) ₃ O ₄ based parent; And a first additive, which is an element added to the parent body and maintains a valence state even when the temperature changes, and a second additive, which is an element whose valency changes according to temperature change.

The first additive may be added in an amount of 8wt% to 12wt% with respect to the total weight of the parent body, and the second additive may be added in an amount of 1wt% to 3wt% with respect to the total weight of the parent body.

The first to second additives are substituted with manganese located in the octahedral position of the cubic spinel crystal structure.

The first additive may include at least one element of boron, zinc, gallium, indium, magnesium, scandium, and beryllium.

The second additive may include at least one element of chromium, bismuth, and tungsten.

The absolute value of the room temperature resistance temperature coefficient of the oxide resistance thin film may have a value of 2.80%/K or more, an absolute value of the high temperature resistance temperature coefficient of 1.90%/K or more, and a specific resistance of 20Ω·cm or less.

An oxide seed layer made of an oxide of at least one metal of nickel, manganese, and copper may be further included between the substrate and the oxide layer.

The thickness of the oxide resistance thin film may have a value ranging from 40 nm to 100 nm.

According to another embodiment of the present invention, a method of manufacturing an oxide-resistant thin film for a bolometer includes a first additive, an element that maintains a valence state even when the temperature changes, and a second additive, an element whose valence changes according to temperature change, as an aromatic hydrocarbon-based organic solvent. The process of preparing an additive solution by dissolving in it; Preparing a preliminary precursor solution by dissolving a nickel oxide organic compound, a manganese oxide organic compound, and a copper oxide organic compound in an aromatic hydrocarbon-based organic solvent; Preparing a mixed solution by mixing the additive solution and the preliminary precursor solution; Diluting the mixed solution in an acetic acid ester-based organic solvent to prepare a precursor solution, forming a precursor layer on a substrate by using the precursor solution in a liquid phase process; And a process of changing the precursor layer into an oxide layer by subsequent heat treatment in an oxidizing atmosphere.

The oxide layer is added to the (Ni,Mn,Cu) ₃ O ₄ based matrix and the matrix, and the first additive is an element that maintains the valence state even when the temperature changes, and the second is an element whose valency changes according to temperature change. It includes an additive, wherein the first additive is added in an amount of 8wt% to 12wt% with respect to the total weight of the parent body, and the second additive may be added in an amount of 1wt% to 3wt% with respect to the total weight of the parent body.

The first additive may include at least one element of boron, zinc, gallium, indium, magnesium, cesium, and beryllium.

The second additive may contain at least one element of chromium, bismuth, and tungsten.

The subsequent heat treatment may be performed in a temperature range of 280°C to 380°C.

Prior to the process of forming the precursor layer, the process of forming a metal layer including at least one metal of nickel, manganese, and copper on the substrate may be further included.

After forming the metal layer and before the process of forming the precursor layer, a process of preliminarily heat-treating the metal layer at a temperature lower than that of the subsequent heat treatment to change into an oxide seed layer may be further included.

In the present invention, the first additive, which is an element that maintains the valence state even when the temperature changes in the (Ni,Mn,Cu) ₃ O ₄ based matrix containing nickel, manganese, and copper, and the agent whose valency changes according to temperature change 2 By adding the additive, the oxide resistance thin film for a bolometer can have a high resistance temperature coefficient not only at room temperature but also at a high temperature of 85°C to 120°C, while simultaneously having a low specific resistance of 20Ω·cm.

Accordingly, it is possible to manufacture a high-sensitivity infrared sensor having excellent precision and improved temperature stability in various environments, such as inside a vehicle having a high temperature due to environmental or device heating.

In addition, among the elements of the first additive, which is an element that maintains the valence state even when the temperature changes, the heat treatment temperature may decrease in the case of an element that acts as an additive for low temperature sintering in bulk ceramics, and the element whose valency changes according to the temperature change. The addition of the phosphorus second additive may reduce the heat treatment temperature due to grain growth due to electron hopping.

Additionally, by forming an oxide seed layer serving as a crystal nucleus between the substrate and the oxide layer to induce grain growth of the oxide layer, the heat treatment temperature required for crystal growth may be further reduced.

Therefore, the heat treatment temperature for crystallization of the oxide resistance thin film having a cubic spinel crystal structure can be formed in a low temperature range of 280°C to 380°C, and damage to the signal processing circuit caused by the high heat treatment temperature and bubbles in the sacrificial layer of organic materials Ring problems can be avoided.

1 is a cross-sectional view showing an oxide resistance thin film for a bolometer according to an embodiment of the present invention.
2 is a graph showing sheet resistance according to temperature according to an embodiment of the present invention.
3 is a flow chart showing a method of manufacturing an oxide resistance thin film according to another embodiment of the present invention.
4 is a cross-sectional view showing the structure of a spin coater according to another embodiment of the present invention.
5 is a cross-sectional view showing a manufacturing process of a bolometer according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only the present embodiments make the disclosure of the present invention complete, and the scope of the invention to those of ordinary skill in the art It is provided to inform you. In order to describe the invention in detail, the drawings may be exaggerated, and the same reference numerals refer to the same elements in the drawings.

Hereinafter, an oxide resistance thin film for a bolometer according to an embodiment of the present invention will be described with reference to FIGS. 1 to 2.

The oxide resistance thin film for a bolometer according to an embodiment of the present invention includes an oxide layer having a cubic spinel crystal structure provided on a substrate, and the oxide layer contains nickel, manganese, and copper (Ni,Mn ,Cu) ₃ O ₄ based parent; And a first additive, which is an element added to the parent body and maintains a valence state even when the temperature changes, and a second additive, which is an element whose valency changes according to temperature change. Here, the first additive may include at least one element of boron, zinc, gallium, indium, magnesium, scandium, and beryllium, and the second additive may include at least one element of chromium, bismuth, and tungsten. I can.

In the oxide layer 120, a first additive, an element that maintains a valence state even when the temperature changes, and a second additive, an element whose valency changes according to temperature change, are added to the parent body of (Ni,Mn,Cu) ₃ O ₄ . It can be made of a cubic spinel crystal structure, and the electrical properties of the cubic spinel crystal structure (AB ₂ O ₄ ) can be affected by electron hopping due to the difference in valence of ions located in the oxygen octahedron, which is a B-site, and electrons Hopping is when electrons are excited and move to an adjacent atom, and electricity flows through the movement of electrons.

In the spinel structure, the oxygen tetrahedron of the A-site has a large lattice spacing, whereas the oxygen octahedrons of the B-site are connected by edges and are the closest in terms of distance, so electron hopping is located in the oxygen octahedron and has one valency difference. It will occur between them.

In the present invention, Mn located at the B-site exists as two cations of Mn ^{3 +} and Mn ^{4 +} , and the charge difference of electrons occurs between the trivalent and tetravalent ions, so that Mn ^{3 +} becomes Mn ^{4 +} and Mn ^{4 +} is changed to Mn ^{+ 3.} In other words, the electrical properties of the thin film can be changed due to the change in the ion charge (electron hopping) that occurs between the Mn ^{3 +} and Mn ^{4 +} ions located at the B-site, and the specific resistance and resistance temperature coefficient depend on the probability of occurrence of electron hopping. Can change.

When the electron hopping probability between Mn ^{3 +} and Mn ^{4 +} increases as the ions of Mn ^{3 +} and Mn ^{4 +} exist in a similar number at the B-site, not only the specific resistance but also the resistance temperature coefficient decreases.(Ni,Mn,Cu) Boron (B ³⁺ ), zinc (Zn ²⁺ ), gallium (Ga ^{3 +} ), indium (In ^{3 +} ), magnesium (Mg ² ), which are elements that maintain the valence state even when the temperature changes in the composition of ₃ O ₄ ^+), scandium (Sc ^{3 +)} and beryllium (Be ^{2 +)} of the first additive as of at least one is when added as an additive substituted with electron Mn ^{3 +} of the oxygen octahedral sites which hopping occurs Mn ^{3 +} and Mn ^{4 The} probability of electron hopping between ⁺ can be reduced, thereby increasing the specific resistance and resistance temperature coefficient at high temperatures.

In more detail, boron, zinc, gallium, indium, magnesium, scandium and beryllium are all elements having one valency, and they have various valences as the first additive in the parent body of (Ni,Mn,Cu) ₃ O ₄ . Unlike an element whose valency changes according to temperature change, as in the first additive of the present invention, when an element capable of maintaining a divalent or trivalent valency state without changing the valence even under external influences such as temperature or pressure is added, a stable valency ( as the element divalent or trivalent atom) that is not involved in the import electrically conductive substituted and Mn ^{+ 3} in the oxygen octahedral sites can reduce the rate of electron hopping between the Mn ^{+ 3} and Mn ^{+ 4.}

Table 1 is a table showing the bonding atoms of the first additive according to an embodiment of the present invention.

Cation The cation bonding atom in the oxygen octahedron is Mn ³⁺ 2.63 B ³⁺ 2.53 Zn ²⁺ 1.73 Ga ³⁺ 2.60 In ³⁺ 2.54 Mg ²⁺ 2.33 Sc ³⁺ 2.55 Be ²⁺ 1.60

Referring to Table 1, the binding atom of the first additive may be smaller than that of the manganese.

Another reason for the increase of the resistance temperature coefficient at room temperature and high temperature due to the addition of the first additive can explain the bonding atom of B-site in the cubic spinel crystal structure. The bond valence is that ions in the compound It shows the valence when bonded with ions. Since it is a function of only the distance between ions, the bond strength in the crystal can be analyzed and predicted.

As can be seen from Table 1, the binding atom of at least one of boron, zinc, gallium, indium, magnesium, scandium, and beryllium, which is the first additive substituted with manganese located at the octahedral position of AB ₂ O ₄ , is It is less than 2.63 and less than 2.60, which is lower than manganese bonding atom. In other words, when the first additive is added to the parent body of (Ni,Mn,Cu) ₃ O ₄ than the case where manganese is located at the octahedral site, when manganese and the first additive are substituted, the bonding atom at the octahedral site decreases. Since the bonding strength between the first additive and oxygen ions becomes weaker than the bonding strength between the oxygen ions and the oxygen ions, the ions of the first additive can easily move.Therefore, the rattling probability of the ions located in the octahedral position can easily occur as the temperature increases. The high temperature resistance temperature coefficient can be higher. However, as the resistance temperature coefficient increases, the specific resistance also increases.

Since the infrared sensor has noise due to heat, the specific resistance must be low in order to lower the noise characteristic of the infrared sensor. In other words, for oxide-resistant thin films whose resistance values change according to temperature changes due to infrared absorption, the higher the specific resistance, the higher the noise of the bolometer, so the sheet resistance of 3 MΩ/squ or less, the thickness of the thin film for the convenience and stability of the device size and process. Is required from 40nm to 100nm, and a low resistivity value of 20Ω·cm or less is required. A room temperature resistance temperature coefficient of at least 2.70%/K absolute and a high temperature resistance temperature coefficient of at least 1.80%/K are required.

On the other hand, when only the first additive is added to the parent body of (Ni,Mn,Cu) ₃ O _{4 in} an amount of 10 wt%, the absolute value of the room temperature resistance temperature coefficient at 25°C is 2.93%/K, high temperature resistance at 85°C. The absolute value of the temperature coefficient is 1.97%/K, which can be applied to the bolometer, but the sheet resistance is 7MΩ or more, and the problem occurs that the appropriate amount of current required to detect the change in resistance according to temperature cannot flow, so it is applied to the bolometer. Difficult to do.

In order to solve this problem, in the embodiment of the present invention, as a second additive, Cr(Cr ²⁺ ,Cr ³⁺ ,Cr ⁴⁺ ,Cr ⁵⁺ ,Cr ⁶⁺ ), Bi(Bi ³⁺ , Bi ⁵⁺ ) , W(W ⁴⁺ , W ⁵⁺ , W ⁶⁺ ), a second additive (Ni,Mn,Cu) ₃ O ₄ was added to the ₃ O ₄ matrix, which is an element that has various valences and changes the valence according to temperature.

Conductivity is generated by electron hopping that occurs when Cr in A-site and Mn in B-site are replaced. For example, conductivity is generated by electron hopping of Cr ³⁺ and Cr ⁴⁺ . Can be reduced.

That is, Cr(Cr ²⁺ ,Cr ³⁺ ,Cr ⁴⁺ ,Cr ⁵⁺ ,Cr ⁶⁺ ), Bi(Bi ³⁺ , Bi ⁵⁺ ), W(W ⁴⁺ , W ⁵⁺ , W ⁶⁺ ) When an element that has various valences such as such elements and whose valency easily changes according to temperature changes is added as an additive, electron hopping between the same cations having different valences occurs while being substituted with the element of the B-site to participate in electrical conductivity. As a result, the electrical conductivity increases and the resistivity of the thin film decreases.

Even when the temperature according to the embodiment of the present invention changes, the resistance temperature coefficient increases due to the effect of the first additive, which is an element that maintains the valence state, thereby improving the electrical properties at high temperatures, and has various valences, so that the valence is increased according to the temperature change. Due to the effect of adding the second additive, which is an element that changes easily, the specific resistance, which is the problem of the first additive, can be greatly reduced.

Therefore, it has a room temperature resistance temperature coefficient of 2.80%/K or more absolute value and a high temperature resistance temperature coefficient of 1.90%/K or more absolute value, and has a specific resistance value of 20 Ω·cm, which is advantageous for application to oxide resistance thin films for bolometers. Can have.

In addition, the oxide layer 130 according to the present invention not only reduces the specific resistance due to electron hopping, but also increases the grain size by adding a second additive, which is an element that has various valences and thus changes easily according to temperature. Can be reduced.

In general, if the resistance of the resistive thin film is too high, it may not be possible to measure the resistance of the resistive thin film at a constant heat treatment temperature, and as the resistance decreases, the resistance measurement and evaluation may become possible at a lower heat treatment temperature.

By adding a second additive, which is an element that has various valences and whose valence is easily changed according to temperature changes, the interfacial energy can be reduced to induce grain growth, and by lowering the resistance, the heat treatment temperature for which resistance can be measured can be lowered.

In addition, among the elements of the first additive, boron and zinc are elements used as additives for low temperature sintering in bulk ceramics, and at least one of boron and zinc may be added to the mother body according to the embodiment of the present invention as the first additive. In this case, since the heat treatment temperature required for crystal growth may be reduced, it may be more effective for low temperature heat treatment.

More specifically, boron has a low melting point in an oxide form, such as boric acid (H ₃ BO ₃ ) and boron trioxide (B ₂ O ₃ ), so when boron is added as a second additive, it may be effective in low-temperature heat treatment.

Therefore, the oxide layer including nickel, manganese, copper, as well as a first additive, an element that maintains a valence state even when temperature changes, and a second additive, an element whose valency easily changes according to temperature changes, has various valences. The addition of the additive or the second additive plays an effective role in reducing the heat treatment temperature required for crystal growth by lowering the resistivity of the resistive thin film.

That is, when the first additive, which is an element that maintains the valence state even when the temperature changes, and the second additive, which is an element whose valency changes according to temperature change, is added, the oxide-resistant thin film having a cubic spielnel crystal structure is 280℃ to 380℃. It can be formed in a low heat treatment temperature range of, and a spinel crystal structure can also be formed.

On the other hand, since the absolute values of the specific resistance and the resistance temperature coefficient tend to be proportional to each other, in order to obtain the low specific resistance and high resistance temperature coefficient values applicable to the bolometer, the first additive and the second additive must be added in an appropriate amount.

Tables 2 to 3 are to find low specific resistance of 20Ω·cm or less, high room temperature resistance temperature coefficient of 2.70%/K or higher, and high temperature resistance temperature coefficient of 1.80%/K or more required for advantageous application to bolometers (Ni, Mn ,Cu) ₃ O ₄ Table showing the electrical properties according to the contents of the first and second additives to be added to the mother body.

Table 2 is a table showing electrical properties according to the content of the second additive (B) and fixing the second additive (Cr) to 2 wt%.

additive
(B) content 0wt% 2wt% 4wt% 6wt% 8wt% 10wt% 12wt% 14wt% 16wt% Resistivity
^(Ω·cm) 4.7 5.8 7.0 8.5 10.7 11.9 18.4 34.7 76.2 Room temperature TCR ^(%/K) -1.38 -1.71 -2.26 -2.69 -2.82 -2.83 -2.81 -2.68 -2.44 High temperature TCR
^(%/K) -1.06 -1.36 -1.63 -1.82 -1.91 -1.92 -1.94 -1.90 -1.88

Table 3 is a table showing electrical properties according to the content of the first additive (B) fixed at 10 wt% and the second additive (Cr).

additive
(Cr) content 0wt% 0.5wt% 1wt% 2wt% 3wt% 4wt% 5wt% Resistivity
^(Ω·cm) 41.8 28.2 18.7 11.9 8.6 6.4 4.2 Room temperature TCR
^(%/K) -2.93 -2.86 -2.85 -2.83 -2.81 -2.75 -2.59 High temperature TCR
^(%/K) -1.97 -1.93 -1.92 -1.92 -1.90 -1.85 -1.76

Referring to Tables 2 to 3, the first additive, which is an element that maintains a valence state even when the temperature changes, is added in an amount of 8 wt% to 12 wt% with respect to the total weight of the parent body, and an element whose valency changes according to temperature change. When the phosphorus second additive is added in an amount of 1 wt% to 3 wt% based on the total weight of the parent body, a low specific resistance of 20 Ω·cm, which is an advantageous condition to be applied to a bolometer, a high room temperature resistance temperature coefficient of 2.80%/K or more, and 1.90 It can be seen that a high temperature resistance temperature coefficient value of %/K or higher can be obtained.

The first additive is (Ni,Mn,Cu) ₃ O ₄ It can be additionally added from the mother body in an amount of 8wt% to 12wt% with respect to the total weight of the mother body.When the first additive is added in an amount greater than 12wt%, not only the spinel single phase but also the secondary phase occurs, thereby increasing the specific resistance. In addition, an additive having one valency can significantly increase the specific resistance while significantly reducing the probability of electron hopping between Mn ^{3 +} and Mn ^{4 +} . That is, when the content is greater than 12wt%, the noise of the bolometer that generates noise due to heat increases due to high specific resistance, making it difficult to implement the characteristics of the bolometer. On the other hand, when the first additive is added in an amount less than 8 wt%, the specific resistance is low and the room temperature resistance temperature coefficient is also high, but the resistance temperature coefficient at high temperature decreases, so the interior of the vehicle having a high temperature due to environmental or device heating. There is a problem in that it is difficult to use a high-sensitivity infrared sensor in a high temperature environment such as.

The second additive (Ni,Mn,Cu) ₃ O ₄ may be additionally added from the parent body in an amount of 1 wt% to 3 wt% based on the total weight of the parent body.If even a small amount of the second additive is added, the resistance thin film is formed at room temperature. The specific resistance decreases rapidly, but when a certain amount or more is added, the specific resistance decreases and then increases again because the spinel crystal structure deviates from the spinel crystal structure in the single phase solid solution range of the spinel crystal structure.

Therefore, by adding a content of 1 wt% to 3 wt% of the second additive to have a low specific resistance value of 20 Ω·cm and a temperature coefficient of resistance, which is advantageous for application to a bolometer, noise generated by heat is minimized.

In addition, since the temperature resolution value of the infrared sensor is inversely proportional to the absolute value of the resistance temperature coefficient, in order to improve the response (Responsivity) and temperature resolution characteristics (Noise Equivalent Temperature Difference, NETD), which are important evaluation factors of the bolometer, The absolute value must be large.

However, if the absolute value of the resistance temperature coefficient, which is a measure of the sensing ability, is less than 1.90%/K, the responsiveness and temperature resolution characteristics of the device are poor due to the absolute value of the low resistance temperature coefficient, making it difficult to implement the characteristics of the bolometer. However, since it is difficult to fabricate a device having high sensitivity, the absolute value of the room temperature resistance temperature coefficient of the oxide resistance thin film may be 2.80%/K and the absolute value of the high temperature resistance temperature coefficient may be 1.90%/K or more.

On the other hand, the larger the absolute value of the resistance temperature coefficient, the better in terms of response and temperature resolution, but an oxide formed by adding the first and second additives of the present invention to the (Ni,Mn,Cu) ₃ O ₄ based matrix As described above, the resistive thin film has (1) the absolute value of the room temperature resistance temperature coefficient of 2.80%/K or more and (2) the high temperature resistance temperature coefficient of 1.90%/K or more, and at the same time, (3) the specific resistance of 20Ω·cm. In order to satisfy all three conditions having a, the absolute values of the room temperature and high temperature resistance temperature coefficients may be 2.80%/K or less, respectively.

Therefore, in the embodiment of the present invention, the oxide resistance thin film may have a high absolute value of the resistance temperature coefficient of 1.90%/K to 2.80%/K at both room temperature and high temperature.

2 shows (Ni,Mn,Cu) ₃ O ₄ Among the first additives, which are elements that maintain a valence state even when the temperature changes in the parent body, B is added in 10 wt% of the total weight of the parent body, and according to the temperature change In the case where Cr is added in 2 wt% of the total weight of the parent body among the second additives, which are elements with varying valency, the values of sheet resistance according to temperature and resistance temperature coefficient values at room temperature of 25°C and high temperature of 85°C are shown. .

B is added in 10 wt% of the first additive and Cr is added in 2 wt% of the second additive, so that it can have a specific resistance of 20 Ω·cm or less, and a thin film thickness of 40 nm to 100 nm for device size and process convenience and stability Is required, it is possible to have a sheet resistance of 3MΩ/squ or less at room temperature and high temperature.

In addition, it can be seen that it has a high resistance temperature coefficient of 2.83%/K absolute at room temperature at 25℃ and 1.92%/K at high temperature at 85℃.

As described above, when the first additive, which is an element that maintains the valence state even when the temperature changes, and the second additive, which is an element whose valency changes according to the temperature change, are added, the oxide resistance thin film of the present invention is not only at room temperature but also at high temperature. It has an absolute value of a high resistance temperature coefficient of 1.90%/K or more and at the same time has a specific resistance of 20Ω·cm or less, which is an advantageous condition for a microbolometer, so it has excellent precision and improved temperature stability at room and high temperatures. Sensor) can be manufactured.

Referring to FIG. 1B, an oxide seed layer 130 made of an oxide of at least one of nickel, manganese, and copper may be further included between the substrate 110 and the oxide layer 120. .

The oxide seed layer 130 provided on the substrate 110 may induce crystal growth of the oxide layer 120 formed on the oxide seed layer 130. Nickel constituting the oxide seed layer 130, When at least one of manganese and copper is oxidized and provided as a crystal nucleus, crystal growth of the oxide layer 120 may be facilitated.

That is, the oxide seed layer 130 provides a crystal nucleus or site to which metal atoms necessary for forming the crystal structure of the resistive thin film 100 having a (Ni,Mn,Cu) ₃ O ₄ composition can be attached. Thus, the resistance thin film 100 can be easily grown.

Accordingly, the oxide seed layer 130 may provide a crystal nucleus required when forming the resistive thin film 100 having a spinel crystal structure, and may provide a position where the crystal of the resistive thin film 100 can grow. Therefore, the resistive thin film 100 having a composition of (Ni,Mn,Cu) ₃ O ₄ can be easily grown, and thus the resistive thin film 100 at a low heat treatment temperature required for crystal growth, for example, at a heat treatment temperature of 380°C or less. ) Can be formed.

3 is a flowchart illustrating a method of manufacturing an oxide resistance thin film according to another exemplary embodiment of the present invention, and FIG. 4 is a cross-sectional view illustrating a structure of a spin coater according to another exemplary embodiment of the present invention.

3 to 4, a method of manufacturing an oxide resistance thin film for a bolometer according to another embodiment of the present invention includes a first additive, an element that maintains a valence state even when the temperature changes, and an element whose valency changes according to temperature change. Preparing an additive solution by dissolving the phosphorus second additive in an aromatic hydrocarbon-based organic solvent (S100); Preparing a preliminary precursor solution by dissolving a plurality of metal oxide organic compounds, which are nickel oxide organic compounds, manganese oxide organic compounds, and copper oxide organic compounds, in an aromatic hydrocarbon-based organic solvent (S200); Preparing a mixed solution by mixing the additive solution and the preliminary precursor solution (S300); Diluting the mixed solution in an acetic acid ester organic solvent to prepare a precursor solution; Forming a precursor layer on a substrate by a liquid process using the precursor solution (S400); And a process of changing the precursor layer into an oxide layer by subsequent heat treatment in an oxidizing atmosphere (S500).

First, the aromatic hydrocarbon-based organic solvent that dissolves a plurality of metal oxide organic compounds and additives, respectively, is benzene (C ₆ H ₆ ), toluene (C ₆ H ₅ CH ₃ ), xylene (C ₆ H ₄ (CH ₃ ) ₂ ) , Naphthalene (C ₁₀ H ₈ ), anthracene (C ₁₄ H ₁₀ ), etc. may be an aromatic hydrocarbon-based organic solvent.

In general, metal oxide organic compounds such as nickel oxide organic compounds having a carboxylate group, manganese oxide organic compounds, and copper oxide organic compounds, and the first and second additives are non-polar substances that are not well soluble in polar solvents such as water. May have a chain length. Materials with long chain lengths or complex hydrocarbon (CH) chains, such as carbon compounds, have nonpolar and hydrophobic properties that are not well soluble in polar solvents. As the length of the chain increases, the hydrophobic properties increase, which makes them resistant to polar solvents. Since the solubility in water is reduced, short chains dissolve well in polar solvents, whereas long chains do not dissolve well in polar solvents.

Therefore, due to the long chain length, the nickel oxide organic compound, manganese oxide organic compound, and copper oxide organic compound, which are hydrophobic due to their small polarity, and the first and second additives are more benzene than polar solvents due to their hydrophobic properties. Since it can be better dissolved in a non-polar solvent such as toluene, xylene, etc., a plurality of pre-precursor solutions and additive solutions can be prepared by dissolving each in an aromatic hydrocarbon-based organic solvent, and as described above, the metal oxide organic compound is an aromatic hydrocarbon. Since it can be more effectively dissolved in the organic solvent, the molar concentration of each pre-precursor solution, that is, the molar concentration of each composition, can be easily adjusted, so that a pre-precursor solution having a desired composition can be easily obtained.

The oxide layer is added to the (Ni,Mn,Cu) ₃ O ₄ based matrix and the matrix, and the first additive, an element that maintains a valence state even when the temperature changes, is included in an amount of 8 wt% to 12 wt%, A second additive, which is an element whose valency changes according to temperature change, may be added in an amount of 1 wt% to 3 wt%.

In the plurality of metal oxide organic compounds so that the oxide layer 120 has the above composition, the plurality of metal oxides may be nickel oxide, manganese oxide, and copper oxide, and the plurality of metal oxide organic compounds are each dissolved in an aromatic hydrocarbon-based organic solvent. The plurality of preliminary precursor solutions thus prepared may be NiO, Mn ₂ O ₃ , and CuO as an example.

Boron (B ³⁺ ), zinc (Zn ^{2 +} ), gallium (Ga ^{3 +} ), indium (In ^{3 +} ), magnesium (Mg ^{2 +} ), scandium (Sc ^{3 +} ), and beryllium (Be ^{2 +} ) are all As an element having one valency, an additive solution can be prepared by dissolving a first additive that maintains a predetermined valence state, such as boron, zinc, gallium, indium, magnesium, scandium, and beryllium, in the aromatic hydrocarbon-based organic solvent described above, When the first additive, which can maintain only one valence state without change in valence even when temperature changes occurs, is dissolved in an aromatic hydrocarbon-based organic solvent and mixed with a plurality of pre-precursor solutions, it is stable in the cubic spinel crystal structure crystallized by subsequent heat treatment. one atom (divalent or trivalent atom) to take as an element which does not participate in the additive in the electrically conductive substituted and Mn ^{3 +} of the oxygen octahedral sites Mn ^{3 +,} and the specific resistance increases to reduce the electron hopping rate between Mn ^{4 +} However, the change in resistance to the movement of electrons (or ions) according to the change in thermal energy may increase, thereby increasing the resistance temperature coefficient at high temperatures.

For the problem due to the addition of the first additive that increases the specific resistance, if a small amount of the second additive, an element whose valency changes according to temperature change, is added to the (Ni,Mn,Cu) ₃ O ₄ matrix having a spinel crystal structure. As Cr enters the B-site and Mn of the B-site moves to the A-site, the substitution of Cr in the A-site and Mn in the B-site is performed, and the central ions of the oxygen octahedron, Cr ³⁺ and Cr ^4+, are Conductivity is generated by electron hopping and specific resistance can be reduced.

In addition, at least one of boron, zinc, gallium, indium, magnesium, scandium, and beryllium of the first additive substituted with manganese located at the oxygen octahedron in the cubic spinel crystal structure crystallized by subsequent heat treatment is a bond of manganese. Since the bonding atom of manganese is lower than 2.60, which is lower than the valence of 2.63, when the additive according to the embodiment of the present invention is added to the parent body of ₃ O ₄ and substituted at the oxygen octahedral site, manganese and oxygen ions Since the bonding force with oxygen ions is weaker than the bonding force between them, the additive ions can move easily, so the rattling probability of metal ions at high temperatures increases, and the high temperature resistance temperature coefficient can be improved.

After preparing the mixed solution, the precursor solution 100 may be prepared by diluting it with an acetic acid ester-based organic solvent (S300).

The mixed solution can be diluted with an acetic acid ester-based organic solvent to prepare a precursor solution 100 coated on the substrate 110. The acetic acid ester-based organic solvent is ethyl acetate (C ₄ H ₈ O ₂ ) and butyl acetate ( It may be an organic solvent such as C ₆ H ₁₂ O ₂ ), methyl acetate (C ₃ H ₆ O ₂ ), cellosolve acetate (C ₆ H ₁₂ O ₃ ), and carbitol acetate (C ₁₀ H ₂₀ O ₄ ).

Acetic acid ester-based organic solvents are acetic acid esters containing oxygen atoms different from aromatic hydrocarbon-based organic solvents in consideration of the contact angle or wettability with the substrate 110 when the prepared precursor solution 100 is applied on the substrate 110. An organic solvent is used, and such an acetic acid ester-based organic solvent can increase the wettability of the substrate 110 and increase surface energy so that effective adhesion to the substrate 110 can occur.

Therefore, by using an acetic acid ester-based organic solvent having an oxygen atom differently from the aromatic hydrocarbon-based organic solvent for preparing the precursor solution, to impart adhesiveness and hydrophilicity to the surface of the substrate 110, the substrate ( 110) and the oxide resistance thin film 340 may have improved adhesion.

In the present invention, the precursor solution 100 is not prepared using one organic solvent, but an aromatic hydrocarbon-based organic solvent and an acetic acid ester-based organic solvent are used, and the precursor solution 100 is prepared by dividing into two steps to prepare a metal oxide organic compound. , It is possible to more effectively dissolve the first additive and the second additive and at the same time improve the adhesion to the substrate 110.

When the precursor solution 100 is prepared by dissolving the metal oxide organic compound, the first additive, and the second additive in an acetic acid ester-based organic solvent without dissolving it in an aromatic hydrocarbon-based organic solvent, adhesion to the substrate 110 is improved. However, since the acetic acid ester-based organic solvent is a polar solvent, the metal oxide organic compound and additive having a long chain length are not well dissolved, so that the oxide resistance thin film 340 may not be manufactured.

After preparing the precursor solution 100, before the process of forming the precursor layer 125 with the precursor solution 100, the substrate 110 includes at least one metal of the plurality of metal oxides. A process of forming a metal layer may be further included, and the metal layer may be formed by a physical vapor deposition method.

The precursor layer 125 (S400) formed by coating the precursor solution on the metal layer (or preliminary oxide seed layer) is oxidized by a subsequent heat treatment to change to the oxide layer 120, so that the metal layer according to the present invention is included in the precursor solution. When at least one of the metal oxides of the metal oxide organic compound is provided as a crystal nucleus in an oxidized state, crystal growth of the oxide layer 120 may be easier.

After forming the metal layer, before the process of forming the precursor layer 125, a process of preliminarily heat-treating the metal layer at a temperature lower than that of the subsequent heat treatment to change to the oxide seed layer 130 may be further included.

At least one of nickel, manganese, and copper in the metal layer is converted into the oxide seed layer 130 to serve as a crystal nucleus. The preliminary heat treatment may be performed in a lower temperature and oxygen atmosphere or atmosphere than the subsequent heat treatment.

At this time, the preliminary oxide seed layer changed by preliminary heat treatment of the metal layer is a spinel crystal structure before the precursor layer 125 is changed to the oxide layer 120 through the subsequent heat treatment, that is, it is not combined with the oxide layer 120. It may be a preliminary oxide seed layer to serve as a seed layer instead of.

Preliminary heat treatment for oxidizing the metal layer to change into a preliminary oxide seed layer is not necessarily performed. Even if the preliminary heat treatment is not performed before the precursor layer 125 is formed, the precursor layer 125 is subsequently heat treated in an oxidizing atmosphere to form the oxide layer When changed to 120, the precursor layer 125 as well as the metal layer may be oxidized to form an oxide seed layer 130, which is an oxidized metal layer.

After changing the metal layer into a preliminary oxide seed layer, the precursor layer 125 may be formed on the substrate 110 by a liquid process using the spin coater and the precursor solution 100 as shown in FIG. 4 (S400).

The substrate 110 on which the preliminary oxide seed layer (not shown) is formed is mounted on the support unit 210 and the precursor solution 100 is administered onto the preliminary oxide seed layer using the nozzle 220. The substrate 110 may be rotated by rotating the support unit 210 while applying the precursor solution 100 on the preliminary oxide seed layer. Accordingly, the precursor solution 100 may be evenly spread and coated on the preliminary oxide seed layer to have a stable thickness.

In addition, since the solvent or organic residue contained in the precursor layer 125 formed by coating the precursor solution 100 may degrade the quality of the resistive thin film 340, the organic solvent or organic residue in the precursor layer 125 is removed. In order to do so, a preliminary subsequent heat treatment may be performed at a lower temperature and a faster holding time than the subsequent heat treatment before performing the subsequent heat treatment.

The precursor layer 125 according to the present invention is formed by a metal-organic decomposition method, but the present invention is not limited thereto, and various liquid process methods may be selected.

After performing a preliminary subsequent heat treatment to remove the organic solvent or organic residues in the precursor layer 125, the precursor layer 125 may be subjected to a subsequent heat treatment in an oxidizing atmosphere to change into the oxide layer 120 (S500). In this case, the subsequent heat treatment may be performed in a temperature range of 280°C to 380°C.

When the precursor layer 125 formed on the preliminary oxide seed layer is subjected to a subsequent heat treatment, the precursor layer 125 is changed to the oxide layer 120, and the precursor layer 125 is changed to the oxide layer 120 through the subsequent heat treatment. At the same time, as the metal oxide crystal particles of the oxide layer 120 and the metal oxide crystal particles of the preliminary oxide seed layer formed under the oxide layer 120 are mutually combined, the preliminary oxide seed layer provides crystal nuclei to the oxide layer 120 It may be changed to an oxide seed layer 130 having a spinel crystal structure.

That is, the nickel, manganese, and copper crystal particles of the oxide layer 120 may diffuse and penetrate into the preliminary oxide seed layer formed under the oxide layer 120, and thus the preliminary oxide seed layer is the same as the oxide layer 120. (Ni,Mn,Cu) ₃ O ₄ It may be made of an oxide seed layer 130 made of a spinel crystal structure having a composition.

The thickness of the oxide layer 120 made of the composition of (Ni,Mn,Cu) ₃ O ₄ and the oxide resistance thin film as the oxide seed layer 130 may range from 40 nm to 100 nm.

When forming the bolometer, in order to minimize heat conduction from the surrounding environment to the resistive thin film 340, the resistive thin film 340 does not contact each other, but the substrate 110 is separated and separated by the spacing space 360. An organic material sacrificial layer 330 such as polyimide (PI) may be formed thereon. In general, in the case of the resistive thin film 340 deposited only by the metal organic decomposition method, the subsequent heat treatment temperature for crystallizing the resistive thin film 340 is Higher than 450°C may cause a bubbling problem that causes the organic material in the sacrificial layer 330 to boil, and damage to the read integrated circuit and the thermal expansion coefficient between the circuit and the resistive thin film 340 due to the high subsequent heat treatment temperature Deformation can occur due to inconsistency. Therefore, in order to completely prevent the damage and bubbling problem of the read integrated circuit caused by the high heat treatment temperature, a low subsequent heat treatment temperature of 380°C or less may be required.

The subsequent heat treatment according to an embodiment of the present invention may be performed in a temperature range of 280°C to 380°C. In the present invention, the first additive added to the parent body not only improves the resistance temperature coefficient at room temperature and high temperature of the thin film, but also In bulk ceramics, the sintering temperature can be reduced with an additive for low temperature sintering, and the heat treatment temperature is reduced by grain growth due to the addition of the second additive, so that the subsequent heat treatment temperature required for crystallization is reduced to 380°C or less without high-temperature heat treatment. The oxide resistance thin film 340 may be stably manufactured.

If the subsequent heat treatment required for crystallization is performed at a temperature of less than 280°C, sufficient thermal energy may not be supplied and the precursor layer 125 may not be changed to the oxide layer 120, and accordingly, the resistive thin film 340 has a spinel crystal structure. Can not be formed. In addition, if the subsequent heat treatment is performed at a temperature exceeding 380°C, as described above, the heat treatment temperature is too high to damage the read integrated circuit, and a problem of bubbling of the sacrificial organic layer 330 may occur.

Therefore, the subsequent heat treatment at 280° C. to 380° C. is a temperature higher than the temperature of subsequent heat treatment at a temperature higher than 450° C., so when the resistance thin film 340 according to the present invention is actually applied to the resistance thin film 340 for a bolometer, a high temperature Since the problem of damage to the read integrated circuit formed on the lower substrate 110 caused by the process of can be fundamentally prevented, and the polyimide bubbling problem of the sacrificial organic layer 330 can be completely solved, the resistive thin film 340 ) Can be easily used to make.

5 is a cross-sectional view showing a manufacturing process of a bolometer according to another embodiment of the present invention.

Referring to FIG. 5, a method of manufacturing a bolometer according to another embodiment of the present invention includes a process of providing a substrate 310 on which a signal processing circuit is formed; Forming a plurality of metal pads 320 that are spaced apart from each other on the upper surface of the substrate 310 to transmit the electrical signals of the signal processing circuit; Forming an organic material sacrificial layer 330 on the substrate 310; Forming an oxide resistance thin film 340 on the sacrificial organic layer 330 by the method of any one of the above; And patterning the organic material sacrificial layer 330 and the oxide resistance thin film 340.

First, a substrate 310 on which a signal processing circuit (not shown) is formed may be provided (FIG. 5A). Such a substrate 310 includes a signal processing circuit for infrared detection therein.

A metal pad 320 electrically connected to the signal processing circuit may be deposited on the substrate 310 on which the signal processing circuit is formed by a physical vapor deposition method such as a sputtering deposition method. The metal pad 320 may be deposited by a physical vapor deposition method, but is not limited thereto and may be deposited by various deposition methods.

After depositing the metal pad 320, a photosensitive solution is applied on the metal pad 320 to expose and develop the metal pad 320 to leave only the desired area by a photolithography process, and then to separate it on the substrate 310 by etching. As a result, a pattern of the metal pad 320 electrically connected to the signal processing circuit may be formed. The metal pad 320 may be connected to the resistive thin film 340 by contacting the conductive material of the support member 350 to be described later.

Then, in order to form the spacing space 360 to be described later, the sacrificial organic layer 330 may be applied on the substrate 310 on which the metal pad 320 is formed by a spin coating method or the like (FIG. 5B. ). The sacrificial organic layer 330 may generally use polyimide that is stable at high temperatures.

After the organic material sacrificial layer 330 is formed, the oxide resistance thin film 340 may be formed on the organic material sacrificial layer 330 by any one of the manufacturing methods of the oxide resistance thin film 340.

The first additive (1) maintains the valence state even when the temperature changes, (2) has a smaller binding atom than the binding atom of the ion located at the octahedral site, and (3) the first additive (boron or zinc) capable of low-temperature sintering ) Is added in an amount of 8wt% to 12wt% to the main composition, and the second additive (1) reduces the interface energy to increase the grain size, (2) reduces the heat treatment temperature, and (2) reduces the specific resistance. 2 Additives are added in an amount of 1 wt% to 3 wt% to the main composition.

Therefore, it has a resistance temperature coefficient of 1.90%/K or higher at room temperature and a resistance temperature coefficient of 2.80%/K or higher even at high temperatures, and at the same time has a low specific resistance of 20Ω·cm or less, which is an advantageous condition for microbolometer application, The heat treatment temperature for crystallization of the thin film may be lowered to a temperature range of 280°C to 380°C.

Since the method of manufacturing the oxide resistance thin film 340 formed on the sacrificial organic layer 330 is the same as the embodiment described with reference to FIGS. 3 to 4, a detailed description will be made with reference to FIGS. 3 to 4.

When the organic material sacrificial layer 330 and the oxide resistive thin film 340 are formed on the substrate 310, a photoresist is applied on the resistive thin film 340, and the organic material sacrificial layer 330 and the resistor are applied only to a desired area by a photolithography process. The organic material sacrificial layer 330 and the resistive thin film 340 may be patterned by exposing, developing, and etching so that the thin film 340 remains, so that a part of the metal pad 320 is exposed (FIG. 5C).

Then, a process of forming a support member 350 having one side connected to the metal pad 320 and the other side connected to the resistance thin film 340 may be further included (FIG. 5D).

The support member 350 connects the metal pad 320 and the resistance thin film 340 to support the resistance thin film 340, and the support member 350 includes at least a pair of upper portions extending from the metal pad 320 It may be formed in the shape of the support member 350.

The resistance thin film 340 may be in contact with a portion of the support member 350 that contacts the lower surface of the protruding portion, and has sufficient mechanical strength to support the resistance thin film 340 while minimizing heat conduction to the surroundings. It is formed to have a small cross-sectional area and may be made of a material having heat conduction. That is, single or complex metals such as aluminum, titanium, and tungsten may be used for conductivity and mechanical stability.

In addition, in forming the support member 350 including a conductive material, the support member 350 not only supports the resistance thin film 340, but also provides the resistance thin film 340 and the metal pad 320 through a conductive material. ), the signal processing circuit can be electrically connected.

Then, the process of removing the sacrificial organic layer 330 may be further included. (Fig. 5e) The sacrificial organic layer is removed by plasma combustion using a reaction gas containing oxygen, as shown in Fig. 5e. A separation space 360 may be formed. The space between the substrate 310 on which the sacrificial organic layer 330 is formed and the resistive thin film 340 remains as a separation space 360, and an optical resonance structure can be provided by the separation distance of the separation space 360. . Accordingly, in order to minimize heat conduction from the surrounding environment to the resistance thin film 340 for a bolometer, the resistance thin film 340 may not be in contact with each other, but may be separated and separated by the spacing space 360.

As described above, in the detailed description of the present invention, specific embodiments have been described, but various modifications are possible without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined by the claims to be described below, as well as by the claims and equivalents.

100: precursor solution 110,310: substrate
120: oxide layer 125: precursor layer
130: oxide seed layer 210: support unit
220: nozzle 320: metal pad
330: organic material sacrificial layer 340: oxide resistance thin film
350: support member 360: spaced apart

Claims (12)

Including an oxide layer of a cubic spinel crystal structure provided on the substrate,
The oxide layer,
(Ni,Mn,Cu) ₃ O ₄ -based matrix containing nickel, manganese and copper; And
A first additive that is an element that maintains a valence state even when the temperature added to the parent body changes, and a second additive that is an element whose valency changes according to temperature change,
The first to second additives are substituted with manganese located in the octahedral position of the cubic spinel crystal structure,
The second additive is an oxide resistance thin film for a bolometer that is added in an amount of 1 wt% to 3 wt% based on the total weight of the parent body.
The method according to claim 1,
The first additive is an oxide resistance thin film for a bolometer containing at least one element of boron, zinc, gallium, indium, magnesium, scandium, and beryllium.
The method according to claim 1,
The second additive is a bolometer oxide resistance thin film containing at least one element of chromium, bismuth, and tungsten.
The method according to claim 1,
The first additive is an oxide resistance thin film for a bolometer added in an amount of 8wt% to 12wt% with respect to the total weight of the parent body.
delete The method according to claim 1,
The oxide resistance thin film,
Oxide resistance thin film for bolometers with an absolute value of 2.80%/K or higher at room temperature resistance temperature coefficient and an absolute value of 1.90%/K or higher high temperature resistance temperature coefficient.
The method according to claim 1,
The oxide resistance thin film is an oxide resistance thin film for a bolometer having a specific resistance of 20 Ω·cm or less.
The method according to claim 1,
An oxide resistance thin film for a bolometer provided between the substrate and the oxide layer and further comprising an oxide seed layer made of at least one metal oxide of nickel, manganese, and copper.
The method according to claim 1,
The oxide resistance thin film for a bolometer has a thickness of 40 nm to 100 nm.
Preparing an additive solution by dissolving a first additive, which is an element that maintains a valence state even when the temperature changes, and a second additive, which is an element whose valence changes according to temperature change, in an aromatic hydrocarbon-based organic solvent;
Preparing a preliminary precursor solution by dissolving a nickel oxide organic compound, a manganese oxide organic compound, and a copper oxide organic compound in an aromatic hydrocarbon-based organic solvent;
Preparing a mixed solution by mixing the additive solution and the preliminary precursor solution;
Diluting the mixed solution in an acetic acid ester-based organic solvent to prepare a precursor solution,
Forming a precursor layer on a substrate in a liquid phase process using the precursor solution; And
Including the process of changing the precursor layer into an oxide layer by subsequent heat treatment in an oxidizing atmosphere,
The oxide layer includes a (Ni,Mn,Cu) ₃ O ₄ based matrix containing nickel, manganese and copper; And
Including the first additive and the second additive added to the parent body,
The second additive is added in an amount of 1 wt% to 3 wt% based on the total weight of the mother body.
The method of claim 10,
The subsequent heat treatment is performed in a temperature range of 280 ℃ to 380 ℃ bolometer oxide resistance thin film manufacturing method.
The method of claim 11,
Before the process of forming the precursor layer,
Forming a metal layer including at least one metal of nickel, manganese, and copper on the substrate; And
A method of manufacturing an oxide resistance thin film for a bolometer, further comprising: pre-heating the metal layer at a lower temperature than the subsequent heat treatment to change it into an oxide seed layer.

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