JP4585938B2 - Film forming method and film forming apparatus - Google Patents

Description

  The present invention relates to a film forming method and a film forming apparatus, and more particularly, to a method that enables film formation under optimum conditions over the entire required region of a substrate surface and an apparatus used therefor.

  Combinatorial synthesis methods started in the fields of organic synthesis and chemical synthesis are now widely applied to inorganic materials and are indispensable for searching for materials with new functions. Furthermore, a method of forming a large number of different thin film materials at a time by applying this technique to various film forming methods is generally called combinatorial film formation, and is being effectively used for searching for functions of various thin film materials. As one of such combinatorial deposition methods, a plurality of types of targets are arranged around the substrate and deposited by sputtering, whereby a thin film whose composition is changed according to the positional relationship with respect to each target is formed on the substrate. There is a method of forming. Thus, the optimum film forming conditions for a desired purpose are searched for by evaluating various characteristics of the thin film formed on the substrate in each region having a different positional relationship with respect to the target.

For example, Japanese Patent Application Laid-Open No. 2002-69613 [Patent Document 1] describes a combinatorial film forming apparatus including a substrate masking mechanism capable of forming a plurality of thin films separately on a single substrate.
JP 2002-69613 A

  As described above, the conventional combinatorial film forming method and the apparatus used therefor have been mainly used for material search. A method and apparatus for easily forming a thin film having desired characteristics over the entire required region of the substrate surface with the optimum film formation conditions searched by combinatorial film formation has not been proposed.

  An object of the present invention is to search for an optimum film formation condition by combinatorial film formation and to easily form a film on the entire surface of the substrate under the optimum film formation condition.

According to the present invention, in order to achieve the above object,
A film forming method for forming a film on a surface of a substrate using film forming materials released from a plurality of film raw materials arranged at different positions ,
A search step of searching a positional relationship between the region and the film raw material corresponding to the substrate surface film having Jo Tokoro characteristic is formed,
A mask position determining step for determining a position of the mask so that an opening of the mask is disposed in a region where the film having the predetermined characteristic is formed;
Said substrate by a Before moving two-dimensionally in parallel, the deposition method characterized by having a film forming step of forming a film having the predetermined characteristics on the substrate surface,
Is provided.

In one embodiment of the present invention, in the searching step, the mask is moved with respect to the film material, and film formation is performed while a film formation region on the surface of the combinatorial film formation substrate is selected. In one embodiment of the present invention, the searching step performs film formation without selecting a film formation region on the surface of the combinatorial film formation substrate.

Furthermore, according to the present invention, in order to achieve the above object,
A film forming apparatus for forming a film on a surface of a substrate using a film forming material released from a film material,
A movable stage that holds the substrate in a two-dimensionally movable manner ;
A mask that is arranged to cover the substrate held by the movable stage, has an opening for selecting a film formation region on the surface of the substrate, and has a variable position relative to the substrate ;
A film raw material holding unit for holding a plurality of film raw materials arranged at different positions and releasing the film forming material from the film raw material;
A control means for controlling the movable stage, the mask and the film material holding unit;
The control means searches for a positional relationship between a region corresponding to the substrate surface where the film having a predetermined characteristic is formed and the film material, and opens a mask in the region where the film having the predetermined characteristic is formed. The movable stage, the mask, and the mask are positioned so as to form a film having the predetermined characteristics on the substrate surface by two-dimensionally translating the substrate. A film forming apparatus for controlling the film material holding unit ;
Is provided.

In one aspect of the present invention, the control means, a storage unit for storing the positional relationship between the region and the membrane material retaining portion corresponding to the substrate surface film having a constant characteristic place which is probe search is formed It has to position the mask such that the in the region corresponding to the substrate surface film having characteristics of the plant constant in the positional relationship stored in the storage unit is formed an opening corresponding. In one aspect of the present invention, the film forming apparatus is provided with a measuring means for measuring the characteristics of the formed film. In one aspect of the present invention, the output of the measuring means is inputted to the control means.

  According to the film forming method and the film forming apparatus of the present invention, the mask is positioned so that the mask opening corresponds to the region of the substrate surface where the film having the desired characteristics in the positional relationship searched by the combinatorial film forming is formed. In addition, by moving the substrate and changing the arrangement of the substrate with respect to the mask opening, by performing film formation while maintaining the positional relationship searched for by combinatorial film formation over the entire required region of the surface of the substrate, It becomes possible to easily form a film on the entire required region of the substrate under the optimum film forming conditions.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view for explaining an embodiment of a film forming apparatus according to the present invention, and FIG. 2 is a schematic view for explaining an embodiment of a film forming method according to the present invention.

  First, the film forming apparatus will be described. In the present embodiment, as shown in FIG. 1, a movable stage 3 that holds a substrate 1 on which a thin film 2 as a film is to be formed, and a mask 4 that is disposed above the movable stage 3 so as to cover the substrate 1. A plurality of (two in the figure) target holding units 6 and 7 as film raw material holding units arranged at different positions above the mask 4, and the movable stage 3, the mask 4 and the target holding unit. The control means 10 for controlling 6 and 7 and the operation means 11 for exchanging signals with the external device with respect to the control means 10 or manually inputting / outputting signals are provided.

  The movable stage 3 is formed so as to be able to translate in the X direction and the Y direction in a horizontal plane, that is, in a plane (X-Y plane) including both the X direction and the Y direction (direction perpendicular to the paper surface) in the drawing. Has been. This parallel movement is made by inputting a control signal from the control means 10 to a drive motor (not shown) built in the movable stage 3. The substrate 1 is held by the movable stage 3 so that the upper surface (that is, the surface on which the thin film 2 is formed) is located in a horizontal plane. Therefore, when the movable stage 3 is moved in the X direction and the Y direction, the position of the upper surface of the substrate 1 is maintained within the same horizontal plane.

  The mask 4 is also formed so as to be able to translate in the X direction and the Y direction in the horizontal plane, that is, in the XY plane in the drawing. This parallel movement is made independent of the parallel movement of the movable stage 3 by inputting a control signal from the control means 10 to a drive motor (not shown) built in the mask 4. Therefore, the position of the mask 4 with respect to the movable stage 3 is variable.

  Examples of the material of the mask 4 include metals, semiconductors, ceramics, and organic materials. The material of the mask 4 is not particularly limited as long as the mask function can be exhibited during the formation of the thin film 2 or combinatorial film formation. A material having the same properties as the substrate 2 can be used as the material of the mask 4.

  An opening 5 for selecting a film formation region on the surface of the substrate 2 is formed in the mask 4. The opening 5 has a fixed size, a variable size, or a size that can be selected from a plurality of sizes (that is, a plurality of mask bodies having openings of different sizes, Any one of them may be used, and the size of the opening 5 is not particularly limited as long as there is no problem in forming the thin film 2 or combinatorial film formation. Since the preferable size of the film formation region having the desired film characteristics is not always constant, it may be preferable to select a plurality of sizes that can be selected from a plurality of sizes, or a size that can be changed.

  Examples of the shape of the opening 5 of the mask 4 include a circular shape, an elliptical shape, a square shape, a rectangular shape, a part thereof, or a combination thereof, which is inconvenient for the formation of the thin film 2 and combinatorial film formation. If there is no, the shape of the opening 5 is not particularly limited.

  The target holding units 6 and 7 can hold sputtering targets made of different materials as film materials. That is, the present embodiment relates to a method in which film formation is performed by a sputtering method.

  However, in the present invention, as the film forming method, in addition to the sputtering method, any method such as a reactive sputtering method, a resistance heating evaporation method, an electron beam evaporation method, a laser ablation method, and the like can be used. If there is no inconvenience for combinatorial film formation, the film formation method is not particularly limited.

  Examples of the material of the film material such as the sputtering target include metals, semiconductors, glass, ceramics, oxides, nitrides, organic materials, and the like. If there is no problem in forming the thin film 2 or combinatorial film formation, The material of the film raw material is not particularly limited.

  The target holding units 6 and 7 can apply energy to the held film raw material in a manner corresponding to the film forming technique, and release the film forming substance from the film raw material in the form of atoms, molecules, ions, and the like. it can. Such operations of the target holding units 6 and 7 are executed based on a control signal input from the control means 10. That is, the target holding parts 6 and 7 also include means for applying such energy. However, in the following description, particularly when referring to the positions of the target holding portions 6 and 7, the positions of the sputtering target as the film raw material are indicated unless otherwise specified.

  The material of the substrate 1 includes any material such as metal, semiconductor, glass, ceramics, organic material, and the material of the substrate is not particularly limited as long as there is no problem in forming the thin film 2 or combinatorial film formation. Absent.

  Of course, the substrate and the sputtering target used in the combinatorial film formation are the substrate 1 on which the thin film having the desired characteristics searched by the combinatorial film formation is formed in the entire required region, and the film formation on the substrate 1. It is the same as the sputtering targets 6 and 7 used in this case.

  The above components are disposed in a vacuum vessel (not shown) as necessary, and the vacuum vessel is evacuated by a vacuum evacuation system (not shown). However, the control means 10 and the operation means 11 may be located outside the vacuum container.

  Next, a film forming method in the film forming apparatus of this embodiment will be described.

  First, combinatorial film formation is performed. At that time, as shown in FIG. 2A, the movable stage 3 holding the combinatorial film forming substrate 1 ′ in a predetermined position is moved in the X direction and the Y direction based on the control signal input from the control means 10. Fix in place. Then, by inputting a control signal from the control means 10 to the target holding units 6 and 7 arranged at predetermined positions, the film-forming substances 8 and 7 can be obtained from the sputtering targets held by the target holding units 6 and 7, respectively. 9 is released. The mask 4 moves in a predetermined manner in the X direction and the Y direction based on a control signal input from the control means 10. As a mode of this mask movement, for example, a combination of X-direction main scanning (intermittent movement) and Y-direction sub-scanning (reciprocating movement) is exemplified, whereby the opening 5 is combined with the combinatorial deposition substrate 1 ′. Sequentially expose the entire surface area of Thereby, the film-forming substances 8 and 9 are deposited on the entire surface of the surface of the combinatorial film-forming substrate 1 'to form a combinatorial thin film 2'. This combinatorial thin film 2 ′ differs in composition, crystal form, etc. in each region according to the positional relationship with respect to the target holding portions 6, 7, and therefore has different film characteristics.

  There are other ways to move the mask, such as those with only parallel movement as described above, and those with other movements (rotation, swinging, etc.) combined with parallel movement, which is inconvenient for combinatorial film formation. If there is no, the mode of mask movement is not particularly limited. However, when it is necessary to make the film thickness of the combinatorial thin film 2 'constant, it is preferable to make the time exposed by the mask opening 5 in each region of the combinatorial thin film 2' constant.

  In the above embodiment, the mask 4 is moved during combinatorial film formation so that the opening 5 sequentially exposes the entire region of the surface of the combinatorial film formation substrate 1 ′. Instead, based on the control signal input from the control means 10, as shown in FIG. 3, the combinatorial film formation is performed in a state where the mask 4 is disposed at a predetermined retracted position (not shown) in the X direction and the Y direction. The film formation may be performed simultaneously on the entire area of the surface of the substrate 1 ′. If there is no inconvenience in combinatorial film formation, whether or not the mask 4 is used at the time of combinatorial film formation is not particularly limited.

  Thereafter, by inputting a control signal from the control means 10, the release of the film forming substances 8 and 9 from the sputtering target held by the target holding units 6 and 7 is stopped.

  Film characteristics are measured for each region of the combinatorial thin film 2 'formed as described above. This measurement can be performed by taking out the combinatorial film forming substrate 1 ′ on which the combinatorial thin film 2 ′ is formed from the film forming apparatus and using an appropriate measuring apparatus. Examples of film characteristics to be measured include optical characteristics, magnetic characteristics, electrical characteristics, catalytic characteristics, thermal characteristics, and the like. If there is no problem in combinatorial film formation, the measured film characteristics are particularly limited. It is not a thing. Examples of the method for measuring film characteristics include optical measurement, magnetic measurement, electrical measurement, catalytic measurement, thermal measurement, crystal structure measurement, composition measurement, etc., and there are no inconveniences in combinatorial film formation. For example, the method for measuring the film characteristics is not particularly limited.

  Based on this measurement result, a region of the substrate surface where a film having a desired characteristic is formed is searched, and the positional relationship between the searched substrate surface region and the target holding units 6 and 7 is determined.

  Next, a film having desired characteristics is formed on the entire region of the surface of the substrate 1. Therefore, first, the substrate 1 is held at a predetermined position of the movable stage 3. Then, a signal of information on the positional relationship between the substrate surface region on which the film having the desired characteristics searched based on the measurement result of the measuring device and the target holding units 6 and 7 is formed is transmitted via the operation unit 11. Input to the control means 10. Based on the input information, the control means 10 searches for the positional relationship between the opening 5 of the mask 4 and the target holding portions 6 and 7 by combinatorial film formation as described above, as shown in FIG. So as to correspond to the positional relationship between the substrate surface region on which the film having the desired characteristics obtained in step 1 is formed and the target holding portions 6 and 7 (that is, in the positional relationship searched by combinatorial film formation). The mask 4 is positioned with respect to the X direction and the Y direction so that the mask opening corresponds to the region of the substrate surface where the film having the desired characteristics is formed.

  Thereafter, by inputting a control signal from the control means 10 to the target holding units 6 and 7, the sputtering targets held by the target holding units 6 and 7 are respectively formed as shown in FIG. Membrane material 8, 9 is released. The movable stage 3 moves in a predetermined manner with respect to the X direction and the Y direction based on the control signal input from the control means 10. Examples of the movable stage moving mode include a combination of X-direction main scanning (intermittent movement) and Y-direction sub-scanning (reciprocating movement), whereby the opening 5 is formed on the surface of the substrate 1. The entire area is exposed sequentially. Thereby, the film-forming substances 8 and 9 are deposited on the entire region of the substrate 1 to form the thin film 2. The entire required area of the thin film 2 has the same film characteristics as a film having desired characteristics formed in the area searched for by combinatorial film formation. That is, the positional relationship between the target surface holding portions 6 and 7 and the substrate surface region where the thin film having the desired characteristics stored in the storage unit of the control means 10 is formed with respect to the entire required region of the surface of the substrate 1. The maintained film formation is performed.

  The movable stage can be moved in any other manner, such as the above-mentioned only parallel movement, or any combination of other movements (rotation, swinging, etc.) in parallel movement. If there is no, there is no particular restriction on the manner of moving the movable stage. However, when it is necessary to make the film thickness of the thin film 2 constant, it is preferable to make the time exposed by the mask opening 5 in each region of the thin film 2 constant.

  In the above embodiment, the measurement of the film characteristics of the combinatorial thin film 2 ′ is performed by using a measuring device outside the film forming apparatus. In the present invention, the film characteristics of the combinatorial thin film 2 ′ are measured by the film forming apparatus. Means may be provided, and film characteristics may be measured while the combinatorial film-forming substrate 1 ′ on which the combinatorial thin film 2 ′ is formed by the measuring means is in the vacuum vessel. That is, the place where the film characteristics are measured is not particularly limited as long as there is no problem in combinatorial film formation. FIG. 4 is a schematic diagram for explaining an embodiment of a film forming apparatus having such a measuring means. 4, members and portions having the same functions as those in FIG. 1 are denoted by the same reference numerals.

  In FIG. 4, the measuring means 12 is equivalent to the measuring apparatus outside the film forming apparatus. Moreover, the control means 10 has the memory | storage part 10a. The film characteristic value Pn (where n indicates the number of the region) of each region of the combinatorial thin film 2 ′ measured by the measuring unit 12 can be stored in the storage unit 10 a in the control unit 10. The storage unit 10a can also store a desired film characteristic value Pr in advance. Then, for example, the control means 10 calculates the absolute value of the difference between Pr and Pn for all the film characteristic values Pn, specifies the thin film area where this is the minimum, and specifies the thin film area specifying information (the position in the X direction and the position). Y-direction position information) can be stored in the storage unit 10a. As a result, the region of the substrate surface where the film having the desired characteristics is formed is searched, and the positional relationship between the searched substrate surface region and the target holding units 6 and 7 is stored.

  In the present embodiment, when measuring the film characteristics of the combinatorial thin film 2 ′ by the measuring means 12, a control signal is input from the control means 10 as necessary, so that the mask 4 is moved to a predetermined retracted position in the X direction and the Y direction. (Not shown).

  In the present embodiment, as described above, the film characteristics of the combinatorial thin film 2 ′ are measured using the measuring means 12, and the control means 10 searches for the region of the substrate surface on which the film having the desired characteristics is formed. 1 is performed, the combinatorial thin film 2 ′ can be formed and the thin film 2 can be formed on the entire required region of the surface of the substrate 1 by the same method as described with reference to FIGS.

  Hereinafter, the present invention will be described with reference to examples. The following examples are carried out by using a film forming apparatus as shown in FIG. 1. Here, a thin film having desired characteristics is formed under the film forming conditions searched for by combinatorial film forming. As described with reference to FIGS. 2 and 3, film formation was performed on the entire surface of the substrate under the condition that the positional relationship between the substrate surface region and the target holding portions 6 and 7 was maintained.

Example 1:
(A) Search for positional relationship between substrate surface region on which thin film having desired characteristics is formed by combinatorial film formation and target holding portion First, as shown in FIG. 2 (a), combinatorial film formation substrate 1 'and movable While moving the mask 4 having the opening 5 while the position of the stage 3 is fixed, the film-forming substances 8 and 9 are released from the sputtering targets held by the plurality of target holding parts 6 and 7, and the combinatorial film-forming substrate is obtained. Combinatorial film formation was performed by depositing on the surface of 1 ′ and forming a combinatorial thin film 2 ′ on the combinatorial film formation substrate 1 ′.

Here, a glass substrate was used as the combinatorial film-forming substrate 1 ′. The film forming method of the film forming apparatus is a sputtering method. Further, the sputtering targets held by the target holding units 6 and 7 were ZnO and WO ₃ .

  Next, after the film formation is completed, the combinatorial film formation substrate 1 ′ is taken out from the film formation apparatus, and the entire surface of the combinatorial film formation substrate 1 ′, that is, the entire surface of the combinatorial thin film 2 ′ is irradiated with light to obtain PL (photoluminescence) emission intensity. Measurement was performed to search for a region having the strongest emission intensity.

(B) Selection of arrangement position of mask opening with respect to target holding portion corresponding to positional relationship between searched substrate surface region and target holding portion Next, as shown in FIG. After setting the glass substrate 1 on the movable stage 3, the opening 5 of the mask 4 was positioned so as to correspond to the substrate region having the strongest PL emission intensity searched for by combinatorial film formation.

(C) Application of Desired Film Formation Conditions to Whole Surface of Substrate Next, as shown in FIG. 2C, with the position of the mask 4 having the opening 5 fixed, the entire surface of the glass substrate 1 for film formation and movable While the stage 3 is translated in the XY plane, the film-forming substances 8 and 9 are released from the sputtering target held by the plurality of target holding units 6 and 7 and deposited on the surface of the substrate 1. A thin film 2 was formed on the entire surface of 1.

  After the film formation is completed, the entire substrate 1 for film formation is taken out from the film formation apparatus, and the PL emission intensity is measured by irradiating light on the entire surface of the substrate, that is, the entire surface of the thin film 2, and is obtained by combinatorial film formation from the entire surface of the substrate. The strongest emission intensity was measured, confirming the effectiveness of the present invention.

Example 2:
(A) Search for positional relationship between surface area of substrate on which thin film having desired characteristics is formed by combinatorial film formation and target holding portion First, as shown in FIG. With the position fixed, the mask 4 having the opening 5 is set at a retracted position (not shown), and the film-forming substances 8 and 9 are released from the sputtering targets held by the plurality of target holding units 6 and 7. A combinatorial film was formed by depositing on the surface of the combinatorial film-forming substrate 1 ′ and forming a combinatorial thin film 2 ′ on the combinatorial film-forming substrate 1 ′.

Here, a SiO ₂ film / Si substrate was used as the combinatorial film-forming substrate 1 ′. The film forming method of the film forming apparatus is an electron beam evaporation method. Furthermore, the targets held by the target holding units 6 and 7 were Fe and Pt.

  Next, after the film formation is completed, the combinatorial film formation substrate 1 ′ is taken out from the film formation apparatus and annealed at 500 ° C., and X-ray diffraction measurement is performed on the entire surface of the combinatorial film formation substrate 1 ′, that is, the entire surface of the combinatorial thin film 2 ′. And searched for the region with the strongest regular lattice reflection intensity.

(B) Selection of arrangement position of mask opening with respect to target holding portion corresponding to positional relationship between searched substrate surface region and target holding portion Next, as shown in FIG. After the glass substrate 1 was set on the movable stage 3, the opening 5 of the mask 4 was positioned so as to correspond to the substrate region having the highest regular lattice reflection intensity searched by combinatorial film formation.

(C) Application of Desired Film Formation Conditions to Whole Surface of Substrate Next, as shown in FIG. 2C, with the position of the mask 4 having the opening 5 fixed, the entire surface of the glass substrate 1 for film formation and movable While the stage 3 is translated in the XY plane, the film-forming substances 8 and 9 are released from the sputtering target held by the plurality of target holding units 6 and 7 and deposited on the surface of the substrate 1. A thin film 2 was formed on the entire surface of 1.

  After the film formation was completed, the entire film formation substrate 1 was taken out from the film formation apparatus, annealed at 500 ° C., and subjected to X-ray diffraction measurement on the entire surface of the substrate, that is, the entire surface of the thin film 2. The strongest regular lattice reflection intensity obtained with the film was measured, confirming the effectiveness of the present invention.

It is a schematic diagram for demonstrating one Embodiment of the film-forming apparatus by this invention. It is a schematic diagram for demonstrating one Embodiment of the film-forming method by this invention. It is a schematic diagram for demonstrating one Embodiment of the film-forming method by this invention. It is a schematic diagram for demonstrating one Embodiment of the film-forming apparatus by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 1 'Combinatorial film-forming substrate 2 Thin film 2' Combinatorial thin film 3 Movable stage 4 Mask 5 Aperture 6, 7 Target holding part 8, 9 Film-forming substance 10 Control means 10a Storage part 11 Operation means 12 Measurement means

Claims (7)

A film forming method for forming a film on the surface of the substrate using the deposition material released from a plurality of film material arranged in positions different from each other,
A search step of searching a positional relationship between the region and the film raw material corresponding to the substrate surface film having Jo Tokoro characteristic is formed,
A mask position determining step for determining a position of the mask so that an opening of the mask is disposed in a region where the film having the predetermined characteristic is formed;
Said substrate by a Before moving two-dimensionally in parallel, the deposition method characterized by having a film forming step of forming a film having the predetermined characteristics on the substrate surface. The film forming method according to claim 1, wherein in the searching step, the mask is moved with respect to the film material, and film formation is performed while a film formation region on a surface of a combinatorial film formation substrate is selected. The film forming method according to claim 1, wherein the searching step performs film formation without selecting a film formation region on the surface of the combinatorial film formation substrate. A film forming apparatus for forming a film on a surface of a substrate using a film forming material released from a film material,
A movable stage for holding the substrate two-dimensionally movable in parallel,
A mask that is arranged to cover the substrate held by the movable stage, has an opening for selecting a film formation region on the surface of the substrate, and has a variable position relative to the substrate ;
A film raw material holding unit for holding a plurality of film raw materials arranged at different positions and releasing the film forming material from the film raw material;
A control means for controlling the movable stage, the mask and the film material holding unit;
The control means searches for a positional relationship between a region corresponding to the substrate surface where the film having a predetermined characteristic is formed and the film material, and opens a mask in the region where the film having the predetermined characteristic is formed. The movable stage, the mask, and the mask are positioned so as to form a film having the predetermined characteristics on the substrate surface by two-dimensionally translating the substrate. A film forming apparatus for controlling the film material holding unit . Wherein said control means has a storage unit for storing positional relationship between the region and the membrane material retaining portion corresponding to the substrate surface film having a constant characteristic place which is probe search is formed, the storage unit It said opening in a region corresponding to the substrate surface film having characteristics of the plant constant is formed in said stored positional relationship is characterized by positioning the mask so as to correspond to, in claim 4 The film-forming apparatus of description. 5. The film forming apparatus according to claim 4 , further comprising a measuring unit for measuring characteristics of the formed film. The film forming apparatus according to claim 6 , wherein an output of the measuring unit is input to the control unit.

Images