JP5589310B2 - Method for producing film-formed product - Google Patents

Description

  The present invention relates to a film formation and a method for producing the film formation.

  Zinc oxide containing nitrogen as an impurity has a p-type conductivity and is known to be transparent to visible light. In Patent Document 1, a zinc target is sputtered on a substrate placed in the vacuum container while introducing a mixed gas containing oxygen and nitrogen in an inert gas such as argon in the vacuum container. A method of forming a zinc oxide film doped with nitrogen is described.

JP 2006-144053 A

  In a conventional vapor deposition method such as sputtering, oxygen and nitrogen are supplied as reaction gases while supplying reactive zinc to the substrate, and conventional reactive film formation supplies a practically sufficient amount of nitrogen atoms. It was difficult to include in zinc oxide as an impurity. The reason may be that the solid solubility limit of nitrogen in zinc oxide is small. Another reason is that zinc easily forms a bond with oxygen preferentially in an atmosphere in which oxygen and nitrogen exist simultaneously, and is difficult to bond with nitrogen.

  In order to solve the above-described problems, in the first aspect of the present invention, a compound film including one or more elements selected from a metal element and a metalloid element, a first element, and a second element is formed. A method for producing a film formation by forming on a surface of a substrate disposed in a film chamber, wherein the film is formed by selecting a first gas containing the first element and a second gas containing the second element. Supplying the gas to the film formation chamber, irradiating the substrate with particles containing the one or more elements through the gas, and the first gas and the first gas in the film formation chamber. And a step of changing the partial pressure ratio of the two gases.

  The partial pressure ratio is changed by switching between a first state in which the first gas is supplied and the second gas is not supplied, and a second state in which the second gas is supplied and the first gas is not supplied. You may let me. The switching between the first state and the second state may be repeated. The first element may be oxygen and the second element may be nitrogen, and the formation of the compound film may be started from the first state.

  The compound film may be formed by a filtered arc ion plating method. During the formation of the compound film, a DC or AC bias voltage may be applied to the substrate. The one or more elements may be one or more elements selected from zinc, silicon, titanium, and aluminum, the first element may be oxygen, and the second element may be nitrogen.

  In a second aspect of the present invention, a substrate and a compound film formed on the substrate and including one or more elements selected from a metal element and a metalloid element, a first element and a second element, And a film-formation product in which the molar ratio of the first element to the second element is changed in the thickness direction of the compound film.

  The molar ratio of the compound coating at the interface with the substrate may be larger than an average value of the molar ratios in the compound coating. The molar ratio may change periodically in the thickness direction of the compound coating. The one or more elements may be one or more elements selected from zinc, silicon, titanium, and aluminum, the first element may be oxygen, and the second element may be nitrogen.

The metal may be zinc, and the nitrogen may be contained at a concentration of 1 × 10 ²¹ [cm ⁻³ ] or more. The metal may be zinc, and the nitrogen may be contained at a concentration equal to or higher than the solid solution limit concentration. The substrate may be made of a polycrystalline or amorphous material. The substrate may be made of resin.

  It should be noted that the above summary of the invention does not enumerate all the necessary features of the present invention. In addition, a sub-combination of these feature groups can also be an invention.

An example of the section of film formation thing 100 is shown roughly. The structure of the film-forming apparatus 200 is shown schematically. The flowchart showing an example of the manufacturing method of a film formation thing is shown.

  Hereinafter, the present invention will be described through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. In addition, not all the combinations of features described in the embodiments are essential for the solving means of the invention.

  FIG. 1 schematically shows an example of a cross section of a film formation 100 according to one embodiment. The film formation product 100 includes a substrate 102 and a compound film 104.

  The substrate 102 may be a substrate whose surface is suitable for forming the compound film 104. The substrate 102 may be a substrate having sufficient mechanical strength as a support substrate for the compound coating 104 formed thereon. The substrate 102 may be, for example, a quartz substrate, an alumina substrate, a SiC substrate, a silicon substrate, a GaAs substrate, a metal substrate, or a resin substrate.

  The substrate 102 may be a single crystal, polycrystalline or amorphous material. For example, when the compound film 104 formed on the substrate 102 is zinc oxide, the zinc oxide is easily grown on the amorphous substrate even when the hexagonal c-axis is oriented in the direction perpendicular to the substrate surface. Therefore, a polycrystalline or amorphous material may be used as the substrate 102. Further, in the method of manufacturing a compound film described later, since the film is formed by ions selected by an electromagnetic filter and having uniform energy, the compound film 104 having good crystallinity is formed even on a polycrystalline or amorphous substrate. it can.

  The compound film 104 may be formed in contact with the surface of the substrate 102. The compound film 104 may include one or more elements selected from metal elements and metalloid elements, a first element, and a second element. The one or more elements selected from the metal elements and metalloid elements may be one or more elements selected from zinc, silicon, titanium, and aluminum. The first element may be oxygen. The second element may be nitrogen. The metal element may be zinc. The compound coating 104 may be zinc oxide containing nitrogen.

  Here, the metal element refers to an element that tends to become a cation when a compound is formed, and refers to an element on the left side of the line connecting boron and astatin in the long-period element periodic table. The metalloid elements are B, Si, Ge, As, Sb, Te, Po, and the like.

The compound coating 104 may be titanium oxynitride. Titanium oxynitride can be used as a photocatalyst with visible light response. The compound coating 104 may be aluminum oxynitride. Aluminum oxynitride can be used as a high-intensity blue phosphor. The compound coating 104 may be sialon (Si ₃ N ₄ —AlN—Al ₂ O ₃ ). Sialon can be used as conductive ceramics or phosphors. The compound coating 104 may be gallium oxynitride. Gallium oxynitride can be used as a blue light emitting diode.

The compound film 104 may contain nitrogen at a concentration of 1 × 10 ²¹ [cm ⁻³ ] or more. The compound coating 104 may contain nitrogen at a concentration equal to or higher than the solid solution limit concentration. The compound coating 104 may contain nitrogen at a concentration of 1 × 10 ²² [cm ⁻³ ] or less.

  It is preferable that the compound coating 104 has a uniform composition distribution in the thickness direction. In the compound film 104, the molar ratio of the first element to the second element may change in the thickness direction. For example, the molar ratio may change periodically in the thickness direction of the compound coating 104. Such a change in molar ratio, particularly a periodic change, can be formed by a manufacturing method described later. When the compound film 104 is zinc oxide, nitrogen can be included more than the solid solution limit concentration by such a structure.

  The molar ratio of the compound coating 104 at the interface with the substrate 102 may be larger than the average value of the molar ratios in the compound coating 104. Such a distribution of elements can be formed by introducing a first gas containing the first element as a reaction gas at the initial stage of film formation in the manufacturing method described later. By adopting such a configuration, the entire crystal of the compound film 104 can have the crystal structure of the compound including the first element and the metal or metalloid element formed in the initial stage of film formation.

  FIG. 2 schematically shows the configuration of a film forming apparatus 200 that manufactures the film-formed product 100. The film forming apparatus 200 includes a film forming chamber 202, a substrate holder 204, a voltage source 208, a cathode 212, a target 214, a trigger 216, an electromagnetic filter 218, a valve 222, a mass flow controller 224, and a valve 226. A gas container 228, a valve 232, a mass flow controller 234, a valve 236, a gas container 238, a rotary pump 242, a valve 244, a turbo-molecular pump 246, a valve 248, a valve 252, and a leak valve. 254 and a leak valve 256.

  The film formation chamber 202 is a vacuum container for forming the compound film 104 on the substrate 102. A load lock chamber (not shown) may be connected to the film forming chamber 202. The substrate can be taken in and out before and after the film formation by a load lock method. By adopting the load lock method, the film forming chamber 202 is normally kept in a vacuum state, and the possibility that unintended impurities are mixed into the thin film can be eliminated as much as possible.

  The substrate holder 204 holds the substrate 102 in the film formation process. The substrate 102 may be placed on the substrate holder 204 with the substrate surface on which the compound coating 104 is grown facing down. The substrate holder 204 may rotate around the Z axis passing through the center of the substrate holder 204 as a rotation axis in the film forming process. By this rotation, a uniform compound film 104 can be generated on the surface of the substrate 102. The substrate holder 204 may include a substrate heating mechanism. The substrate heating mechanism can improve the uniformity of the compound coating 104 by heating the substrate 102 and promoting thermal diffusion of atoms constituting the compound coating 104 formed on the substrate 102.

  The voltage source 208 may apply a bias voltage to the substrate 102. Although a DC voltage source is shown as the voltage source 208 in FIG. 2, the voltage source 208 may be an AC voltage source. The bias voltage value is preferably applied in the range of about 0 to −200 V that does not induce reverse sputtering. By applying a bias voltage to the substrate, the energy of ions among the particles incident on the substrate is controlled, so that the incident ions diffuse from the surface of the growing compound film 104 to the inside and receive energy from the incident ions. The diffusion of atoms contained in the compound coating 104 can be promoted to improve the crystallinity and uniformity of the compound coating 104. For example, when the compound film 104 is zinc oxide, the crystallinity of zinc oxide is reduced by adding nitrogen. However, by applying a bias voltage to the substrate, the reduction in crystallinity due to the addition of nitrogen can be compensated.

  The cathode 212 is installed below the film formation chamber 202. A target 214 serving as a supply source of the metal or metalloid element of the compound coating 104 is fixed to the cathode 212. A trigger 216 is provided next to the target 214. The electromagnetic filter 218 is provided between the film formation chamber 202 and the cathode 212.

  At the time of film formation, an electric current is applied while the trigger 216 is in contact with the surface of the target 214, and then the trigger 216 is separated from the target 214, thereby generating an arc discharge between the target 214 and the trigger 216. Arc discharge generates particles 217 in various states such as target metal or metalloid ions, neutral atoms, clusters, and macro particles. By supplying these particles to the substrate 102, the compound coating 104 can be formed. However, each particle 217 has various energies. In order to obtain a uniform and high-quality compound coating 104, it is desirable to form a film using ions with uniform energy.

  The electromagnetic filter 218 can pass only ions having a certain energy among the particles 217 knocked out from the target 214 by arc discharge by changing the magnetic intensity. The ions selected by the electromagnetic filter 218 have uniform energy. By forming a film using ions having uniform energy after passing through the electromagnetic filter 218, orientation growth of crystals is promoted. The formed compound film 104 is uniform, has large crystal grains, and has high carrier mobility.

The valve 222, the mass flow controller 224, the valve 226, and the gas container 228 constitute a supply system for an oxidizing gas that becomes a reactive gas. The oxidizing gas may be an example of the first gas. The oxidizing gas flow rate can be arbitrarily controlled by the mass flow controller 224 in the range of 0 to 200 sccm. The mass flow controller 224 can temporally modulate the flow rate of the oxidizing gas according to the control signal. Although oxygen is shown in FIG. 2 as the oxidizing gas, the oxidizing gas may be another reactive gas composed of molecules containing oxygen atoms. For example, examples of the oxidizing gas include O ₂ , O ₃ , and H ₂ O.

The valve 232, the mass flow controller 234, the valve 236, and the gas container 238 constitute a supply system of a nitriding gas that becomes a reactive gas. The nitriding gas may be an example of the second gas. The nitriding gas flow rate can be arbitrarily controlled by the mass flow controller 234 in the range of 0 to 200 sccm. The mass flow controller 234 can temporally modulate the flow rate of the nitriding gas according to the control signal. Although FIG. 2 shows nitrogen as the nitriding gas, the nitriding gas may be another reactive gas composed of molecules containing nitrogen atoms. For example, N ₂ and NH ₃ can be exemplified as the nitriding gas.

  At the time of film formation, the oxidizing gas and the nitriding gas introduced into the film formation chamber 202 are dissociated by arc plasma, and exist in a highly reactive state such as oxygen or nitrogen atoms, ions, and radicals. These become an oxidation source and a nitridation source. The metal or metalloid supplied from the target 214 is oxidized or nitrided before reaching the substrate 102 and synthesized as a compound on the substrate.

  The rotary pump 242, the valve 244, the turbo-molecular pump 246, the valve 248, the valve 252, the leak valve 254, and the leak valve 256 constitute a vacuum system that controls the degree of vacuum in the film formation chamber 202. In the initial stage of evacuation, the valve 252 is opened and a vacuum is drawn using the rotary pump 242, but after reaching a predetermined degree of vacuum, the valve 252 is closed, the valves 244 and 248 are opened, and the turbo molecular pump 246 is turned on. Use and continue to evacuate. With the above vacuum system, the degree of vacuum in the film formation chamber 202 can be controlled within a predetermined range during film formation.

  FIG. 3 is a flowchart showing an example of a method for manufacturing the film formation 100. The method of manufacturing the film-formed product 100 includes a step S310 of performing a preparatory work, a step S320 of evacuating the film forming apparatus, a step S330 of installing the substrate in the film forming apparatus, a step S340 of generating arc discharge, Step S350 for supplying the first gas, Step S360 for starting the supply of the second gas at the same time as stopping the first gas, Step S370 for starting the supply of the first gas at the same time as stopping the second gas, Arc discharge And step S380 for stopping the introduction of gas, and step S390 for taking out the substrate.

  In step S <b> 310 of performing the preparatory work, the target 214 is set on the cathode 212. In the case where the film formation 100 is repeatedly manufactured using the same target as the source of the metal or metalloid element, the target 214 is set once, and then in the subsequent manufacturing process until it is completely consumed. This step S310 can be omitted.

  In step S320 of evacuating the film forming apparatus, the film forming chamber 202 is evacuated. Open the valve 252 and draw a vacuum using the rotary pump 242, but after reaching a predetermined degree of vacuum, close the valve 252 and open the valves 244 and 248 and continue to draw a vacuum using the turbo-molecular pump 246. . The degree of vacuum in the film formation chamber 202 is controlled within a predetermined range by the above vacuum system. When the film forming product 100 is repeatedly manufactured by the load lock method, the vacuum degree of the film forming chamber 202 is maintained by the vacuum system.

  In step S330 of placing the substrate on the film forming apparatus, the substrate 102 is placed on the substrate holder 204. If the load lock method is used, the substrate 102 can be taken in and out while maintaining the degree of vacuum in the film formation chamber 202. The substrate holder 204 may be rotated. A bias voltage may be applied to the substrate 102 by the voltage source 208.

  The substrate 102 may be heated by a substrate heating mechanism provided in the substrate holder 204 or may not be heated. In the present manufacturing method, since the film is formed by ions selected by the electromagnetic filter and having uniform energy, the compound film 104 having a good crystallinity can be formed without heating the substrate 102. Therefore, in the present manufacturing method, a heat-sensitive resin substrate can also be used as the substrate 102.

  In step S340 of generating an arc discharge, an electric current is applied while the trigger 216 is in contact with the surface of the target 214, and then the trigger 216 is separated from the target 214, thereby generating an arc discharge between the target 214 and the trigger 216. Let Among the target element particles 217 generated by the arc discharge, ions selected by the electromagnetic filter 218 reach the substrate 102 and contribute to the formation of the compound film 104.

  In step S350 of supplying the first gas, an oxidizing gas is introduced. The valve 222 and the valve 226 are opened, and the oxidizing gas is introduced from the gas container 228 while the flow rate is controlled by the mass flow controller 224. This stage may begin in synchronization with the start of discharge in stage S340. By introducing the oxidizing gas, a thin film of a metal or metalloid oxide is formed on the substrate 102.

  In step S360, in which the supply of the second gas is started simultaneously with the stop of the first gas, the supply of the oxidizing gas is stopped and the nitriding gas is introduced. The valve 222 is closed to stop the oxidizing gas, and at the same time, the valve 232 and the valve 236 are opened, and the nitriding gas is introduced from the gas container 238 while controlling the flow rate by the mass flow controller 234. At this stage, the partial pressure ratio of the oxidizing gas and the nitriding gas in the film formation chamber 202 can be changed. By introducing the nitriding gas, a metal or metalloid nitride thin film is formed on the metal or metalloid oxide thin film formed in step S350.

  In step S370 in which the supply of the first gas is started simultaneously with the stop of the second gas, the supply of the nitriding gas is stopped and the oxidizing gas is introduced. The valve 232 is closed to stop the nitriding gas, and at the same time, the valve 222 is opened, and the oxidizing gas is again introduced from the gas container 228 while controlling the flow rate by the mass flow controller 224. At this stage, the partial pressure ratio of the oxidizing gas and the nitriding gas in the film formation chamber 202 can be changed. By introducing the oxidizing gas, a metal or metalloid oxide thin film is further formed on the metal or metalloid nitride thin film formed in step S360.

  Step S360 and step S370 may be repeated to form the compound film 104 in which the metal or metalloid oxide and the metal or metalloid nitride are stacked. The thickness of each layer of the stacked structure can be controlled by the flow rate and introduction time of the reaction gas in each stage.

  As described above, the oxidizing gas or nitriding gas introduced into the film formation chamber 202 is dissociated by the arc plasma and exists in a highly reactive state such as oxygen or nitrogen atoms, ions, radicals. When the oxidizing gas and the nitriding gas are introduced at the same time, the film formation rate becomes very slow as compared with the case where the respective gases are introduced alone. It is considered that this is because the dissociated oxygen and nitrogen contribute to the reaction with the metal or metalloid, and also the unintentional reaction between oxygen and nitrogen occurs at the same time to generate NOx gas. In order to prevent this, in this embodiment, an oxidizing gas and a nitriding gas are alternately introduced in a pulse shape. This is realized by repeating steps S360 and S370.

  By shortening the time of steps S360 and S370, the thin film formed in each step can be controlled to a thickness in the range of 1 to 10 nm. In this case, the metal or metalloid oxide and metal or metalloid nitride thin film is a very thin layer having a thickness of only a few to a dozen atoms. When step S360 and step S370 are repeated, atoms of metal or metalloid, oxygen and nitrogen are mutually diffused between the adjacent metal or metalloid oxide layer and metal or metalloid nitride layer. The growth of the compound film 104 proceeds while the clear interface between the metal or metalloid oxide layer and the metal or metalloid nitride layer disappears. As a result, the compound film 104 in which the constituent elements such as metal or metalloid, oxygen, and nitrogen are uniformly distributed can be formed on the substrate 102.

  The compound film 104 having a desired composition can be formed by controlling the time of the steps S350, S360, and S370 and the gas flow rate in each step. The compound film 104 having a uniform composition in the film thickness direction can be formed by controlling the conditions at each stage described above, but the compound whose composition is modulated in the film thickness direction by intentionally changing the conditions at each stage. A coating 104 can also be formed.

  The resulting compound film 104 has a crystal structure affected by a relatively thick layer of a metal or metalloid oxide and a metal or metalloid nitride. For example, when forming the compound film 104 containing nitrogen as an impurity on a zinc oxide crystal, metal zinc is used as the target 214, and the time of step S370 is made longer than the time of step S360 and the flow rate of the nitriding gas. Then, a zinc oxide compound coating 104 containing nitrogen can be formed by alternately laminating zinc oxide thin films and zinc nitride thin films under the condition of increasing the flow rate of the oxidizing gas.

  In step S380 for stopping the arc discharge and gas introduction, the current applied to the trigger 216 is stopped to stop the arc discharge. The valve 226 and the valve 222 are closed, and the supply of the oxidizing gas is stopped.

  In step S <b> 390 of taking out the substrate, the film formation product 100 in which the compound film 104 is formed on the substrate 102 is taken out from the film formation chamber 202. If the load lock method is used, the film-formed product 100 can be taken out while maintaining the degree of vacuum in the film formation chamber 202. Thus, the manufacturing process of the film formation 100 is completed. In the case where the film forming product 100 is continuously manufactured, the above-described manufacturing process may be repeated from the step 330 of placing the next substrate 102 in the film forming apparatus.

  In the present embodiment, the example of the manufacturing method of the film forming product 100 using the filtered arc ion plating film forming apparatus shown in FIG. 2 has been described. It is not limited to the membrane method. This manufacturing method can also be carried out in other physical vapor deposition methods such as vacuum deposition or sputtering.

(Example)
Using the film forming apparatus 200 having the configuration shown in FIG. 2, a zinc oxide thin film containing nitrogen was formed according to the manufacturing method shown in FIG. A synthetic quartz glass wafer was used as the substrate 102. As the target 214, 99.9% zinc was used. Oxygen gas was used as the oxidizing gas, and nitrogen gas was used as the nitriding gas.

  A synthetic quartz glass wafer was placed on the substrate holder 204, and the substrate holder 204 was rotated. A bias voltage of −100 V was applied to the substrate 102 using the voltage source 208. An arc current of 50 A was applied to the trigger 216 to cause an arc discharge on the zinc target 214. In synchronization with the start of discharge, oxygen gas was introduced into the film formation chamber 202. After introducing oxygen gas at a flow rate of 50 sccm for 20 seconds, the supply of oxygen gas was stopped simultaneously with the supply of oxygen gas being stopped. The flow rate and supply time of nitrogen gas were 5 sccm and 10 seconds, respectively. Thereafter, the supply of nitrogen gas was stopped and simultaneously the supply of oxygen gas was started again.

  In the stage of supplying oxygen gas, the flow rate and supply time are 50 sccm and 20 seconds, respectively, and a thin film of about 1 nm can be formed. In the stage of supplying nitrogen gas, the flow rate and supply time are 5 sccm and 10 seconds, respectively, and a thin film of about 0.5 nm can be produced. The two steps were repeated alternately, and after 3600 seconds, arc discharge and gas introduction were stopped, and the substrate was taken out.

As a result of measuring the thickness of the produced thin film using a stylus type step meter, the film thickness was 200 nm. The average film formation rate was 3.3 nm / min, which was high-speed film formation. As a result of analyzing the composition of the produced thin film by secondary ion mass spectrometry (SIMS), nitrogen was uniformly contained in the film thickness direction at 1 × 10 ²¹ / cm ³ .

(Comparative example)
Other conditions are the same except that the method of introducing oxygen gas and nitrogen gas is different from the above embodiment. As in the above example, oxygen gas and nitrogen gas were not alternately introduced in a pulsed manner, and oxygen gas and nitrogen gas were simultaneously introduced in synchronism with arc discharge to form a film for 3600 seconds. The flow rates of oxygen gas and nitrogen gas were 50 sccm and 5 sccm, respectively.

As a result of measuring the thickness of the produced thin film using a stylus step meter, the film thickness was 40 nm. The average film formation rate was 0.67 nm / min, which was very low compared to the above examples. As a result of analyzing the composition of the produced thin film by secondary ion mass spectrometry (SIMS), nitrogen was uniformly contained in the film thickness direction at 4 × 10 ²⁰ / cm ³ . It indicates that the amount of nitrogen element introduced into zinc oxide as an impurity was less than half that of the above example. In another paper, an example in which nitrogen of 2 × 10 ²⁰ / cm ³ is introduced when a zinc oxide film is formed by a laser ablation method is described. This value is one fifth of the nitrogen content introduced by the above example.

  According to the above-described embodiment, a compound film sufficiently containing an impurity element can be obtained. Moreover, the compound film can be formed at high speed by the above-described production method, and the production efficiency can be greatly increased. For example, a zinc oxide thin film sufficiently containing nitrogen as an impurity can be formed at high speed.

  As mentioned above, although this invention was demonstrated using embodiment, the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiment. It is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.

  The order of execution of each process such as operations, procedures, steps, and stages in the apparatus, system, program, and method shown in the claims, the description, and the drawings is particularly “before” or “prior to”. It should be noted that the output can be realized in any order unless the output of the previous process is used in the subsequent process. Regarding the operation flow in the claims, the description, and the drawings, even if it is described using “first”, “next”, etc. for convenience, it means that it is essential to carry out in this order. It is not a thing.

DESCRIPTION OF SYMBOLS 100 Film formation 102 Substrate 104 Compound film 200 Film formation apparatus 202 Film formation chamber 204 Substrate holder 208 Voltage source 212 Cathode 214 Target 216 Trigger 217 Particle 218 Electromagnetic filter 222 Valve 224 Mass flow controller 226 Valve 228 Gas container 232 Valve 234 Mass flow controller 236 Valve 238 Gas container 242 Rotary pump 244 Valve 246 Turbo-molecular pump 248 Valve 252 Valve 254 Leak valve 256 Leak valve

Claims (6)

By forming a compound film containing one or more elements selected from a metal element and a metalloid element, a first element, and a second element on the surface of the substrate disposed in the film formation chamber, A method of manufacturing
One or more gases selected from a first gas containing the first element and a second gas containing the second element are supplied to the film formation chamber, and particles containing the one or more elements are contained in the gas. A film forming step of passing through the substrate and irradiating the substrate;
Changing a partial pressure ratio of the first gas and the second gas in the film forming chamber;
With
The one or more elements are zinc, the first element is oxygen, and the second element is nitrogen;
The film formation step is divided into a plurality of film formation steps according to the step of changing the partial pressure ratio, and by controlling the thickness of the film formed in the plurality of film formation steps to 1 to 10 nm or less, A method for producing a film-formation product for forming the compound film having a uniform composition in a film thickness direction. A first state in which the first gas is supplied and the second gas is not supplied;
A second state in which the second gas is supplied and the first gas is not supplied;
The method for producing a film-formed product according to claim 1, wherein the partial pressure ratio is changed by switching between the two. The method for producing a film-formed product according to claim 2, wherein the switching between the first state and the second state is repeated. Method for producing a film-forming product according to claim 3 in which the formation of the pre-title compound film, starting from the first state. Method for producing a film-forming material according to claims 1 to any one of claims 4 to the compound film is formed by filtered arc ion plating method. During formation of the compound coating, on the substrate, a manufacturing method of the film-forming material according to claims 1 to any one of claims 5 to apply a bias voltage of DC or AC.

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