JP2012172180A - Sputtering device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sputtering device capable of making a metal sulfide, metal selenide or metal telluride thin film on a substrate or a base material with a large area at room temperature.SOLUTION: The sputtering device 10 includes a substrate 20, at least one cathode 40, and at least one target 50 arranged near the cathode inside a chamber, and has a separation plate 60 for partitioning a space partially surrounded by the substrate and the target and the other space inside the chamber, and a heating means 70 for heating the separation plate. Components in a thin film deposited on the substrate are prevented from evaporating again and spreading inside the chamber by the separation plate, the vapor of the components which have evaporated again is prevented from adhering to the separation plate by heating the separation plate by the heating means further, and a vapor pressure is maintained in a high state.

Description

  The present invention relates to a sputtering apparatus, and more particularly to a sputtering apparatus capable of forming a metal sulfide, metal selenide or metal telluride thin film on a substrate.

The sputtering apparatus evaporates the metal particles in a film formation atmosphere by colliding (sputtering) particles having high energy against a target containing a metal to be produced as a thin film in a vacuum chamber, and this is evaporated onto the substrate. It is an apparatus for producing a thin film by depositing.
When a thin film containing two or more kinds of metal elements is produced on a substrate using a sputtering apparatus, an alloy or a mixture (mixed sintered body) of these metals is used as a target, or a cathode and a metal are paired as a unit. Thus, a target configured by arranging a plurality of units is used.

For example, in Patent Document 1, by providing a shield facing the substrate transport direction between two targets, metal particles evaporated by sputtering are prevented from diffusing into the chamber and causing deterioration of the quality of the thin film. A sputtering apparatus is disclosed.
By the way, in recent years, metal sulfides, metal selenides, and metal tellurides, which are direct transition type semiconductors, are attracting attention as materials for light absorption layers (photoelectric conversion layers) of solar cells, instead of conventional silicon.
For example, a chalcopyrite (chalcopyrite) -based material called CIGS made of copper (Cu), indium (In), gallium (Ga), and selenium (Se) has a higher light absorption rate than general crystalline silicon. It is known that a high photoelectric conversion efficiency of at least% can be achieved.
In addition, Cu (In, Ga) (Se, S) ₂ , CuInS _{2 and the} like are known as CIGSS and CIS thin films, respectively, and include copper (Cu), zinc (Zn), tin (Sn), and sulfur (S). A CZTS thin film made of CdTe and a CdTe thin film made of cadmium (Cd) and tellurium (Te) are also attracting attention.

JP 2010-1565 A

However, the above prior art has the following problems.
That is, a thin film containing a metal sulfide, a metal selenide or a metal telluride is industrially produced by a vapor deposition method or a method of post-sulfiding, post-selenizing or post-telluricizing a metal thin film. The reason is that sulfur, selenium, and tellurium have higher vapor pressures than other metal elements.
If an attempt is made to produce a thin film containing metal sulfide, metal selenide or metal telluride using a conventionally known sputtering apparatus, sulfur, selenium and tellurium contained in the thin film deposited on the substrate during the film forming operation It is difficult to control the composition of the thin film because it selectively re-evaporates.
In addition, since the metal vapor once evaporated from the thin film adheres to the inside wall of the chamber at room temperature, it is difficult to stay as a reactive gas having a high pressure in the film forming atmosphere.
In addition, since sulfur, selenium, and tellurium existing in a single form in the target are selectively evaporated as particles in the film-forming atmosphere by sputtering, there is also a problem that target composition deviation occurs with time.

  The sputtering method is suitable for industrially producing a sufficiently large amount of a compound thin film on a substrate having a large area. If it is possible to produce the metal sulfide, the metal selenide or the metal telluride thin film at a low cost, no solution has been found at present.

  In view of such problems, the present invention solves the problem that occurs particularly during the film formation of metal sulfide, metal selenide or metal telluride in the sputtering method. It is an object to provide a sputtering apparatus capable of producing a telluride thin film.

The present invention is a sputtering apparatus including, in a chamber, a substrate, at least one cathode, and at least one target disposed in the vicinity of the cathode, and a space partially surrounded by the substrate and the target in the chamber. A separation plate for partitioning another space and a heating unit for heating the separation plate are provided.
In addition, the target contains sulfur, selenium, or tellurium in a proportion larger than the stoichiometric composition ratio of the thin film formed or deposited on the substrate.
Further, the target contains more metal sulfide, metal selenide or metal telluride, or a mixture containing two or more of these than the stoichiometric composition ratio of a thin film formed or deposited on the substrate. It is characterized by.
Further, the present invention is characterized in that supply means for supplying sulfur, selenium, tellurium, or a mixture containing two or more of these in a solid or gas state in a space partially surrounded by the substrate and the target is provided.
Further, the target is a metal, and a gas containing hydrogen sulfide, hydrogen selenide or hydrogen telluride, or a mixture containing two or more of these is used as a reactive gas.

In the present invention, a space surrounded by the substrate and the target is partitioned by a separation plate to prevent components in the thin film deposited on the substrate from re-evaporating and diffusing into the chamber, and further heating the separation plate. Since the vapor of the component in the thin film re-evaporated by heating by means is prevented from adhering to the separator, the vapor pressure can be maintained at a high level. As a result, the evaporation rate can be reduced, the re-evaporation of components in the thin film can be suppressed, and the composition ratio of the thin film can be easily controlled.
In particular, sulfur, selenium or tellurium having a high vapor pressure is contained in the target in a proportion larger than the stoichiometric composition ratio of the thin film to be produced or deposited on the substrate, or a metal is used as a reactive gas and sulfide as a reactive gas. By using hydrogen or the like, it is possible to industrially produce a large amount of metal sulfide, metal selenide, or metal telluride thin film having a large area and a specific ratio of sulfur, selenium, or tellurium by sputtering.
Further, the components in the target are also evaporated as particles in the film formation atmosphere by sputtering. Therefore, when targeting sulfur having a high vapor pressure, selenium or tellurium, or a mixture containing two or more of these, sulfur existing in a single form in the target by using a separation plate and heating means. , Selenium and tellurium can be prevented from selectively evaporating, and target composition deviation can be suppressed.
Furthermore, as a secondary effect, when depositing a compound containing a metal such as zinc with a high vapor pressure, re-evaporation of the metal with a high vapor pressure from the substrate can be suppressed, and the composition deviation between the metals can be reduced. Can also be suppressed.

In particular, the target contains a metal sulfide, a metal selenide or a metal telluride, or a mixture containing two or more of these in a target that is larger than the stoichiometric composition ratio of the thin film formed or deposited on the substrate, Alternatively, by using the supply means, the vapor pressure of a metal such as sulfur can be maintained at a higher level, and the component ratio of the thin film can be brought close to the stoichiometric composition ratio.
In the present invention, the separation plate is disposed in the vicinity of the substrate and the target, and the separation plate is heated by the heating means to prevent the diffusion of vapor, and further, the vapor is prevented from adhering to the separation plate. . Therefore, it is not only preferable in terms of heating efficiency compared to a structure that prevents vapor from adhering to the inner wall of the chamber by heating the chamber itself without providing a separation plate. Since various equipment such as cooling means is attached, it is physically difficult to heat the chamber.
Moreover, the component re-evaporated from the thin film and the component evaporated from the target vary depending on the components of the thin film and the target, and may include both metal elements and non-metal elements.
In the present invention, the separator plate is not installed for the purpose of shuttering, which prevents the metal jumping out of the target from being spattered outside the desired range, but the vapor component of the thin film or the component evaporated from the target is contained in the chamber. It is intended to prevent the inside from diffusing and coming into contact with a low-temperature member in the chamber for adhesion. Therefore, the purpose of the shutter member known as the prior art and the separation plate of the present invention are greatly different.
In addition, in this specification, “a space surrounded by the substrate and the target” includes a space in the vicinity of the target surface and a space including a path until particles evaporated from the substrate by sputtering are deposited on the substrate. Shall be.

Longitudinal cross-sectional perspective view showing the configuration of the sputtering apparatus of the first embodiment The longitudinal cross-sectional perspective view which shows the structure of the sputtering device of 2nd embodiment. Longitudinal sectional perspective view showing the configuration of the sputtering apparatus of the third embodiment The figure which shows an example of the solar cell production apparatus which incorporated the sputtering device in the production line The figure which shows an example of the structure of the CZTS type | system | group solar cell produced with the solar cell production apparatus

[First embodiment]
A first embodiment of the sputtering apparatus 10 of the present invention will be described.
As shown in FIG. 1, the sputtering apparatus 10 in the present embodiment is a so-called magnetron sputtering apparatus, and includes a substrate 20, a holding unit 30, a cathode 40, a target 50, a separation plate 60, a heating unit 70, a magnet unit 80, and the like. The chamber is generally composed of a chamber that is stored in a vacuum state and an exhaust device that evacuates the chamber. Illustration of the chamber and the exhaust device is omitted.
The substrate 20 is a member on which a thin film is formed, and is made of glass, plastic, metal foil, or the like.
The holding unit 30 is a member that holds the substrate 20 and also serves as an anode, and holds the substrate 20 so that the surface of the substrate 20 faces downward. Note that the holding unit 30 may have a function of heating the substrate 20, thereby improving the quality of the thin film. Moreover, it is good also as a structure which can reciprocate the holding | maintenance part 30 within a horizontal surface. In this case, the components in the thin film can be made uniform.
The cathode 40 is disposed below the substrate 20 so as to face the surface of the substrate 20 held by the holding unit 30.

The target 50 is disposed in the vicinity of the cathode 40 and is used for supplying a thin film material such as metal to the surface of the cathode 40. In the present embodiment, the target 50 is mounted on a target mounting table 41 above the cathode 40. . In the present embodiment, there is only one target.
The components of the target 50 are not particularly limited and can be variously changed according to the components of the thin film to be produced. For example, a metal sulfide, metal selenide or metal telluride thin film is produced by non-reactive sputtering. In that case, a known inert gas such as argon may be used using sulfur, selenium or tellurium, a mixture containing two or more of these, or a target 50 containing these as a main component. In addition, a mixture containing two or more of metal sulfide, metal selenide, or metal telluride may be used as the target 50.
When a thin film of metal sulfide, metal selenide or metal telluride is produced by reactive sputtering, the metal 50 or a target 50 having the main component is used, and hydrogen sulfide or hydrogen selenide is used as a reactive gas. Alternatively, hydrogen telluride or a gas containing a mixture containing two or more of these may be used.
In addition, if necessary, target a metal sulfide, a metal selenide or a metal telluride, or a mixture containing two or more of them, which is larger than the stoichiometric composition ratio of a thin film formed or deposited on a substrate. It may be included.

The separation plate 60 is a member for partitioning a space partially enclosed by the substrate 20 and the target 50 and another space in the chamber. In the present embodiment, since there is only one target 50, the separation plate 60 partitions the space between the substrate 20 and the target 50 from other spaces.
In the present embodiment, four separation plates 60 are arranged on the front, rear, left and right sides of the target 50. Since FIG. 1 is a longitudinal sectional view of the sputtering apparatus 10, the front separation plate 60 does not appear in the drawing.
The lower part of each separation plate 60 is placed on the upper part of the casing 11 of the sputtering apparatus 10. In addition, a holding unit 30 is disposed on the upper part of each separation plate 60, and the substrate 20 held by the holding unit 30 is in a state where the front, rear, left and right are surrounded by the separation plates 60.
In this way, the space surrounded by the substrate 20 and the target 50 is partitioned by the separation plate 60, thereby preventing the metal vapor evaporated from the thin film from diffusing into the chamber.
Note that the separation plate 60 does not necessarily need to completely partition the space surrounded by the substrate 20 and the target 50 from other spaces, that is, it is not necessary to ensure airtightness. For example, between the separation plates 60 or between the separation plates 60 An air gap may exist between 60 and the holding unit 30.

The heating means 70 is for heating the separation plate 60, and in the present embodiment, a heater made of nichrome wire is attached so as to cover the outer surface of each separation plate 60. By heating the separation plate 60 with the heating means 70, even if the metal once deposited on the substrate 20, for example, sulfur, selenium, and tellurium re-evaporates, the vapor attached to the separation plate 60 adheres to the surface of the separation plate 60. Without any problem, the reaction gas can stay in the film formation atmosphere.
In addition, a shielding plate may be disposed so as to cover the periphery of the separation plate 60, and the heating unit 70 may be disposed between the separation plate 60 and the shielding plate, thereby protecting the heating unit 70 and improving the thermal efficiency. .
For example, when the substrate 20 is made of a material having low heat resistance such as a plastic film, it is necessary to appropriately adjust the distance between the heating means 70 and the substrate 20 or to provide a water cooling device in the vicinity of the substrate.
A known method can be used as the heating means 70. For example, when using heat generated by energizing a resistor, a metal heating element such as a platinum wire, silicon carbide, a PTC thermistor, a polyimide sheet heating element, a sheath heater, or the like can be used in addition to the nichrome wire. Further, a heating jacket containing a heat transfer fluid may be used, and an infrared heater, a ceramic heater, or the like may be used.

The magnet unit 80 is a mechanism for increasing the plasma density by generating a closed loop-shaped magnetic field in the vicinity of the surface of the target 50 and improving the film forming speed, and is disposed below the target 50.
Since the magnet unit 80 in the present embodiment has the same configuration as that used in a general magnetron sputtering apparatus, a detailed description is omitted, but a yoke 82 and a magnetic circuit 83 are housed in a cathode box 81. The upper portion of the cathode 40 box is covered with a target mounting table 41.
The waveform of the voltage applied to the target 50 can be variously selected, such as a pulse waveform obtained by modulating direct current, alternating current, positive and negative direct current, and a waveform obtained by rectifying alternating current. However, when a thin film is produced industrially in large quantities, In consideration of stability, a DC or pulse waveform is preferable.

表１は右の枠内に示す各元素及びガスの温度と蒸気圧の関係を示したものである。
表１から分かる通り、硫黄(S)、セレン(Se)及びテルル(Te)は銅(Cu)、インジウム(In)、ガリウム(Ga)等と比較して蒸気圧が高いため、例えばスパッタリングによる製膜作業中に真空状態で１００℃程度の熱を受けただけで基板２０上の薄膜から再蒸発してしまい、薄膜の組成比の制御が難しくなるという問題がある。

物質表面からのその構成物質の蒸発速度はHertz-Knudsenの式（数１）で表される。
ここで、Ｐ^*：与えられた物質の与えられた空間温度Ｔでの飽和蒸気圧、Ｐ：蒸発源前面での蒸発物質の蒸気圧、ｄＮ：物質表面から構成物質が蒸発している系で時間ｄｔの間に単位面積の物質表面から蒸発する蒸気分子の数、ｍ：蒸気分子の分子量、α：蒸発係数、ｋ：ボルツマン定数である。 For example, the operation principle when a Cu ₂ ZnSnS ₄ (CZTS) thin film is produced using the sputtering apparatus 10 having the above-described structure will be described.

Table 1 shows the relationship between the temperature and vapor pressure of each element and gas shown in the right frame.
As can be seen from Table 1, sulfur (S), selenium (Se) and tellurium (Te) have higher vapor pressure than copper (Cu), indium (In), gallium (Ga), etc. There is a problem that the film is re-evaporated from the thin film on the substrate 20 just by receiving heat of about 100 ° C. in a vacuum state during the film operation, and it becomes difficult to control the composition ratio of the thin film.

The evaporation rate of the constituent material from the material surface is expressed by the Hertz-Knudsen equation (Equation 1).
Where P ^* : saturated vapor pressure at a given space temperature T of a given substance, P: vapor pressure of the evaporated substance in front of the evaporation source, dN: a system in which constituent substances are evaporated from the substance surface The number of vapor molecules that evaporate from the surface of the substance of a unit area during time dt, m: molecular weight of vapor molecules, α: evaporation coefficient, and k: Boltzmann constant.

Here, in the re-evaporation from the thin film deposited on the substrate 20 in question, the thin film corresponds to the evaporation source. Therefore, for example, when the metal sulfide is once decomposed into atomic sulfur by a sputtering process or the like and deposited on the substrate, a thin film which has a high saturated vapor pressure P ^{* of} sulfur and is an evaporation source as described above. Since the vapor pressure P of sulfur on the front surface is low, the evaporation rate dN / dt increases.
In order to increase the sulfur vapor pressure P, the sulfur vapor is introduced into the film forming atmosphere, and the member acting as a getter pump in a vacuum, that is, in the chamber, the sulfur vapor may adhere and adhere. It is sufficient to remove a certain low temperature member.
Therefore, in the present invention, the space surrounded by the substrate 20 and the target 50 is partitioned by the separation plate 60 to prevent sulfur vapor from diffusing into the chamber, and the separation plate 60 is further heated to separate the separation plate 60. The sulfur vapor is prevented from adhering to 60 and the state where the sulfur vapor pressure P is high is maintained.
Thereby, the gettering exhaust speed can be suppressed and the evaporation speed dN / dt can be reduced, so that the re-evaporation of sulfur in the thin film can be suppressed.

Further, the sulfur component in the target 50 is also evaporated as particles in the film forming atmosphere by sputtering. Therefore, by using the separation plate 60 and the heating means 70, it is possible to prevent sulfur, selenium and tellurium existing in a single form in the target from being selectively evaporated, and to suppress target composition deviation.
Furthermore, as a secondary effect, when depositing a compound containing a metal such as zinc with a high vapor pressure, re-evaporation of the metal with a high vapor pressure from the substrate can be suppressed, and the composition deviation between the metals can be reduced. Can also be suppressed.
In the case of a metal having a low saturated vapor pressure such as copper (Cu), indium (In), gallium (Ga), etc., re-evaporation from the thin film does not occur because P ^* -P becomes negative in the thin film deposition process. .

[Second Embodiment]
Next, a second embodiment of the sputtering apparatus of the present invention will be described. In addition, about the location which becomes the same structure as said 1st embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.
As shown in FIG. 2, the sputtering apparatus 12 of the present embodiment has a configuration in which a heating unit 70 is built in a separation plate 60.
By doing in this way, it can contribute to size reduction of the sputtering apparatus 12, obtaining the effect similar to using the said shielding board, ie, the protection of the heating means 70, and the improvement effect of thermal efficiency.

[Third embodiment]
Next, a third embodiment of the sputtering apparatus of the present invention will be described. In addition, about the location which becomes the same structure as said 1st and 2nd embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.
As shown in FIG. 3, the sputtering apparatus 13 of the present embodiment is a solid or gas containing sulfur, selenium or tellurium, or a mixture containing two or more of them in a space partially surrounded by a substrate 20 and a target 50. Supplying means 90 for supplying in the state is provided.
The supply unit 90 includes a supply source 91, a supply path 92, and a second heating unit 93.
One or more of sulfur (S), selenium (Se) and tellurium (Te) having a high vapor pressure are stored in the supply source 91 in a solid or gas state as appropriate.
One end of the supply path 92 is connected to the supply source 91, and the other end is in a space partially surrounded by the substrate 20 and the target 50 through an opening 94 provided on the side surface of the separation plate 60. Has reached.

The above-mentioned metal such as sulfur stored in the supply source 91 is heated by the second heating means 93 made of nichrome wire or the like, and does not adhere to the supply path 92, and is not adhered to the supply path 92 by the substrate 20 and the target 50. It introduce | transduces as a vapor | steam in the film-forming atmosphere pinched | interposed.
Since the vapor pressure P can be increased by introducing sulfur or the like into the film formation atmosphere as described above, the evaporation rate dN / dt can be reduced to suppress the re-evaporation of sulfur or the like in the thin film. it can.
In each of the above embodiments, the sputtering apparatus uses the magnetron sputtering method. However, the present invention is not limited to this. For example, a bipolar, tripolar or quadrupolar sputtering method, an ECR (Electron Cyclotron Resonance) sputtering method, a high frequency sputtering method is used. Methods, reactive sputtering methods, bias sputtering methods, and other known sputtering methods may be used.
In addition to the fixed type cathode, a known type of cathode such as a rotating type cathode may be used, and the number of cathodes may be one or more.
Also, in the so-called counter target sputtering method in which two or more targets are arranged to face each other and the substrate is arranged at a position orthogonal to the target surface, a space surrounded by the substrate and two or more targets and other spaces are separated. The effect of the present invention can be achieved by providing the separation plate and the heating means at a partitioning position, for example, a plane including the target surface and from the side surface of the target to the substrate surface.
In general, since the facing target sputtering method has a low deposition rate, it is presumed that it is suitable for thin films that require frequent inspection and control of thin film components during film formation.
FIG. 4 shows an example of a solar cell production apparatus in which the sputtering apparatus of the present invention is incorporated in a production line, and FIG. 5 shows an example of the structure of a CZTS solar cell produced by this solar cell production apparatus.

[Example 1 non-reactive sputtering]
Next, an example of forming a sulfide thin film using the sputtering apparatus described in the first embodiment will be described.
A sulfide sintered body having a composition ratio of Cu ₂ ZnSnS ₄ was used as a target, and borosilicate glass was used as a substrate. Argon was used as the discharge gas.
After evacuating the chamber to a sufficiently low pressure, the separator was heated to 400 ° C. and the substrate was similarly heated to 400 ° C. by a heater as a heating means. Thereafter, argon was introduced as a discharge gas so that the pressure was 0.4 Pa. Thereafter, AC power having a frequency of 13.56 MHz was applied to the target at a power of 200 W to form a film. After the film formation for a predetermined time was completed, the discharge was stopped and the heating of the separation plate and the substrate was stopped. After the temperature was sufficiently lowered, the substrate was taken out to the atmospheric pressure in the chamber.

[Comparative example non-reactive sputtering]
Next, an example of forming a sulfide thin film using a general sputtering apparatus that does not include a separation plate and heating means will be described as a comparative example.
A sulfide sintered body having a composition ratio of Cu ₂ ZnSnS ₄ was used as a target, and borosilicate glass was used as a substrate. Argon was used as the discharge gas.
After evacuating the chamber to a sufficiently low pressure, only the substrate was heated to 400 ° C. Thereafter, argon was introduced as a discharge gas so that the pressure was 0.4 Pa. Thereafter, AC power having a frequency of 13.56 MHz was applied to the target at a power of 200 W to form a film. After the film formation for a predetermined time was completed, the discharge was stopped and the heating of the substrate was stopped. After the temperature of the substrate was sufficiently lowered, the substrate was taken out with the atmospheric pressure in the chamber.
Table 2 shows the X-ray diffraction measurement results of the sulfide thin film prepared in Example 1, and Table 3 shows the X-ray diffraction measurement results of the sulfide thin film prepared in the comparative example. Table 4 shows the measurement results of the sulfur content in the sulfide thin film produced in Example 1.
From Table 2 and Table 3, it can be seen that by using the sputtering apparatus of the present invention, the sulfide thin film exhibits better crystallinity than the case of using a general sputtering apparatus.
Further, from Table 4, it can be confirmed that a predetermined amount of sulfur is contained in the thin film by using the sputtering apparatus of the present invention.

[Example 2 Reactive Sputtering]
A sintered metal having a composition ratio of Cu ₂ ZnSn was used as a target, and borosilicate glass was used as a substrate. Further, a mixed gas of argon and hydrogen sulfide was used as the discharge gas.
After evacuating the chamber to a sufficiently low pressure, the separator was heated to 400 ° C. and the substrate was similarly heated to 400 ° C. by a heater as a heating means. Thereafter, a 60% hydrogen monosulfide-40% argon mixed gas was introduced as a discharge gas so that the pressure was 0.4 Pa. Thereafter, AC power having a frequency of 13.56 MHz was applied to the target at a power of 200 W to form a film. After the film formation for a predetermined time was completed, the discharge was stopped and the heating of the separation plate and the substrate was stopped. After the temperature was sufficiently lowered, the substrate was taken out at atmospheric pressure in the chamber.
Also for the sulfide thin film produced in this example, it was confirmed that the X-ray diffraction and sulfur content measurement results were comparable to those in Example 1.

  The present invention is a sputtering apparatus capable of producing a metal sulfide, metal selenide or metal telluride thin film on a large-area substrate, and has industrial applicability.

DESCRIPTION OF SYMBOLS 10 Sputtering apparatus 12 Sputtering apparatus 13 Sputtering apparatus 20 Substrate 30 Holding part 40 Cathode 50 Target 60 Separation plate 70 Heating means 80 Magnet unit 90 Supply means 91 Supply source 92 Supply path 93 Second heating means

Claims (5)

A sputtering apparatus comprising a substrate, at least one cathode, and at least one target arranged in the vicinity of the cathode in a chamber,
In the chamber, a sputtering apparatus comprising: a separation plate for partitioning a space partially enclosed by the substrate and the target from another space; and a heating unit for heating the separation plate.   2. The target comprising sulfur, selenium or tellurium in a proportion larger than the stoichiometric composition ratio of a thin film produced or deposited on a substrate, or a mixture containing two or more of these in the target. The sputtering apparatus as described.   The target includes a metal sulfide, a metal selenide, a metal telluride, or a mixture containing two or more of these in a larger amount than the stoichiometric composition ratio of a thin film formed or deposited on a substrate. The sputtering apparatus according to claim 1.   A supply means for supplying sulfur, selenium or tellurium, or a mixture containing two or more of them in a solid or gas state into a space partially surrounded by the substrate and the target. The sputtering apparatus as described in any one of 1-3. 2. The gas according to claim 1, wherein the target is a metal, and a gas containing hydrogen sulfide, hydrogen selenide or hydrogen telluride, or a mixture containing two or more of these is used as a reactive gas. Sputtering equipment

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