WO2022185966A1

WO2022185966A1 - Film forming method and film forming apparatus

Info

Publication number: WO2022185966A1
Application number: PCT/JP2022/006909
Authority: WO
Inventors: 暁志布瀬; 一希山田; 敬並川
Original assignee: 東京エレクトロン株式会社; ダイキン工業株式会社
Priority date: 2021-03-05
Filing date: 2022-02-21
Publication date: 2022-09-09
Also published as: JP2022135709A

Abstract

This film forming method includes the following steps (A) to (D). (A): To prepare a substrate that has a surface having a first region in which a first film is exposed and a second region in which a second film is exposed, the second film being formed of a material that is different from the material of the first film. (B): To selectively form an organic film on the second region among the first region and the second region by supplying an organic compound that contains a perfluoroether group to the surface of the substrate. (C): To selectively form a first object film on the first region among the first region and the second region by using the organic film, which has been formed on the second region. (D): To etch the organic film by having the organic film and a material of the first object film react with each other.

Description

Film forming method and film forming apparatus

The present disclosure relates to a film forming method and a film forming apparatus.

The selective deposition method described in Patent Document 1 selectively forms a passivation layer from a vapor phase reactant on the first surface of the first surface and the second surface which are made of different materials. The first surface is formed of metal and the second surface is formed of dielectric. The passivation layer formed on the first surface is then used to selectively deposit a layer of interest on the second surface from the vapor phase reactants. The substrate is then exposed to plasma to remove the passivation layer. The plasma contains oxygen. The plasma may contain hydrogen and the like, and may contain argon and the like.

The atomic layer deposition method described in Patent Document 2 prepares a substrate including a first surface and a second surface of different materials, the substrate including a passivation layer on the second surface. A deposition cycle is then performed comprising alternately and sequentially contacting the substrate with a first precursor and a second reactant comprising oxygen. A second reactant reacts with the first precursor to form a dielectric material on the first surface. The passivation layer is ashed with the second reactant during each deposition cycle. The second reactant is an oxidizing agent.

The atomic layer deposition method described in Patent Document 3 is a method for selectively depositing oxide thin films on dielectric surfaces compared to metal surfaces. The method performs a deposition cycle that includes alternately and sequentially contacting the substrate with a first precursor and a second reactant. The second reactant includes a plasma formed in a gas that does not contain oxygen, for example a plasma that is formed in a gas that contains hydrogen. A passivation layer is selectively deposited on the metal surface prior to beginning the deposition cycle and etched by the second reactant during the deposition cycle.

Japanese Patent Application Laid-Open No. 2018-137435 Japanese Patent Application Laid-Open No. 2019-195059 Japanese special table 2020-520126

One aspect of the present disclosure provides a technique of selectively forming a target film in a desired region using an organic film, and etching the organic film through a reaction between the material of the target film and the organic film.

A film formation method of one aspect of the present disclosure includes the following (A) to (D). (A) Prepare a substrate having, on its surface, a first region where a first film is exposed and a second region where a second film made of a material different from the first film is exposed. (B) supplying an organic compound containing a perfluoroether group to the surface of the substrate to selectively form an organic film on the second region of the first region and the second region; (C) Using the organic film formed in the second region, a first target film is selectively formed in the first region of the first region and the second region. (D) reacting the material of the first target film with the organic film to etch the organic film;

According to one aspect of the present disclosure, a target film can be selectively formed in a desired region using an organic film, and the organic film can be etched by a reaction between the material of the target film and the organic film.

FIG. 1 is a flow chart showing a film forming method according to one embodiment. FIG. 2 is a flow chart showing an example of the subroutine of step S4. FIG. 3A is a diagram showing an example of step S1. FIG. 3B is a diagram showing an example of step S3. FIG. 3C is a diagram showing an example in the middle of step S4. FIG. 3D is a diagram showing an example of step S4 subsequent to FIG. 3C. FIG. 3E is a diagram showing an example of step S6. FIG. 4 is a plan view showing a film forming apparatus according to one embodiment. 5 is a cross-sectional view showing an example of the first processing section of FIG. 4. FIG. 6A is a diagram showing depth distributions of Co atoms and C atoms in Experimental Examples 1 and 2. FIG. 6B is a diagram showing the depth direction distribution of Al atoms in Experimental Examples 1 and 2. FIG. 6C is a diagram showing the depth direction distribution of F atoms in Experimental Examples 1 and 2. FIG. 7A is a diagram showing the concentration distribution of various atoms in the depth direction in Experimental Example 3. FIG. FIG. 7B is a diagram showing XPS spectra when the cut depth reaches D1 or D2 in Experimental Examples 3 and 4. FIG. 8A is a diagram showing the concentration distribution of various atoms in the depth direction in Experimental Example 5. FIG. 8B is a diagram showing XPS spectra before the substrate surface is ground in Experimental Examples 3 and 5. FIG. 9 is a diagram showing the concentration distribution of various atoms in the depth direction in Experimental Example 6. FIG.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In addition, in each drawing, the same reference numerals are given to the same or corresponding configurations, and explanations thereof may be omitted.

First, a film forming method according to the present embodiment will be described with reference to FIGS. 1 to 2 and FIGS. 3A to 3E. The film forming method includes steps S1 to S6 shown in FIG. 1, for example. Note that the film formation method may include at least steps S1, S3, and S4, and may not include steps S2 and S6, for example. Further, the film forming method may include steps other than steps S1 to S6 shown in FIG.

Step S1 in FIG. 1 includes preparing a substrate 1, as shown in FIG. 3A. Preparing the substrate 1 includes, for example, placing a carrier C on the film forming apparatus 100 shown in FIG. A carrier C accommodates a plurality of substrates 1 .

The substrate 1 has an underlying substrate 10 such as a silicon wafer or a compound semiconductor wafer. Compound semiconductor wafers are not particularly limited, but are, for example, GaAs wafers, SiC wafers, GaN wafers, or InP wafers.

A substrate 1 has a dielectric film 11 formed on a base substrate 10 . A conductive film or the like may be formed between the dielectric film 11 and the underlying substrate 10 . The dielectric film 11 is, for example, an interlayer insulating film. The interlayer insulating film is preferably a low dielectric constant (Low-k) film.

The dielectric film 11 is not particularly limited, but is, for example, a SiO film, SiN film, SiOC film, SiON film, or SiOCN film. Here, the SiO film means a film containing silicon (Si) and oxygen (O). The atomic ratio of Si and O in the SiO film is not limited to 1:1. The same applies to the SiN film, SiOC film, SiON film, and SiOCN film.

The substrate 1 also has a metal film 12 formed on the base substrate 10 . Although the metal film 12 is not particularly limited, it is, for example, a Cu film, a Co film, a Ru film, or a W film.

As shown in FIG. 3A, the substrate 1 has, on its surface, a first area A1 where the dielectric film 11 is exposed and a second area A2 where the metal film 12 is exposed. The film exposed in the first region A1 is also called the first film. Also, the film exposed in the second region A2 is also called a second film. The first film and the second film may be made of different materials. The first area A1 and the second area A2 are provided on one side of the substrate 1 in the thickness direction (for example, on the surface side).

The number of first regions A1 is one in FIGS. 3A to 3E, but may be plural. For example, two first regions A1 may be arranged so as to sandwich the second region A2. Similarly, the number of second regions A2 is one in FIGS. 3A to 3E, but may be plural. For example, two second regions A2 may be arranged so as to sandwich the first region A1. Although the first area A1 and the second area A2 are adjacent in FIGS. 3A-3E, they may be separated.

The substrate 1 may have a third area (not shown) on its surface in addition to the first area A1 and the second area A2. The third region is a region where the third film made of a material different from that of the first film and the second film is exposed. The third area may be arranged between the first area A1 and the second area A2, or may be arranged outside the first area A1 and the second area A2.

For example, the substrate 1 may further have a third region where a barrier film (not shown) is exposed on its surface. In this case, the third area is formed between the first area A1 and the second area A2. The barrier film is formed along the recess and suppresses metal diffusion from the metal film 12 to the dielectric film 11 . Although the barrier film is not particularly limited, it is, for example, a TaN film or a TiN film. Here, the TaN film means a film containing tantalum (Ta) and nitrogen (N). The atomic ratio of Ta and N in the TaN film is not limited to 1:1. The same is true for the TiN film.

In addition, the substrate 1 further has a fourth region on its surface where the liner film (not shown) is exposed. A fourth area is formed between the second area A2 and the third area. A liner film is formed over the barrier film to assist in the formation of the metal film 12 . A metal film 12 is formed on the liner film. Although the liner film is not particularly limited, it is, for example, a Co film or a Ru film.

Step S2 in FIG. 1 includes cleaning the surface of the substrate 1. For example, step S2 uses a device for irradiating the surface of the substrate 1 with ultraviolet rays to generate ozone in the device. The organic matter adhering to the surface of the substrate 1 can be ashed with ozone. Moreover, the surface of the metal film 12 can be moderately oxidized with ozone. If the natural oxide film is removed in advance as will be described later, the density of oxygen atoms becomes the desired density. As a result, a dense organic film 13 can be formed on the surface of the metal film 12 in step S3, which will be described later.

Note that step S2 may include supplying a reducing gas such as H ₂ gas to the surface of the substrate 1 to remove a natural oxide film formed on the surface of the substrate 1 . The natural oxide film is formed on the surface of the metal film 12, for example. The reducing gas may be plasmatized. Also, the reducing gas may be used by being mixed with a rare gas such as Ar gas.

In step S3 of FIG. 1, the organic compound is supplied to the surface of the substrate 1, and as shown in FIG. form 13.

The method of forming the organic film 13 is a physical vapor deposition method, a chemical vapor deposition (CVD) method, or an atomic layer deposition (ALD) method. When the molecular weight of the organic compound is large, it is preferable to use physical vapor deposition (PVD).

The material of the organic film 13 is the same as the so-called Self-Assembled Monolayer (SAM) material. The organic compound that is the material of the organic film 13 is represented by the following formula (1) or (2), for example.

In formula (1), each Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. The number of carbon atoms in the straight or branched chain of the "alkyl group having 1 to 16 carbon atoms" is preferably 1 to 6, more preferably 1 to 3. The "alkyl group having 1 to 16 carbon atoms" is particularly preferably a linear alkyl group having 1 to 3 carbon atoms.

Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms. Further, Rf is more preferably a CF ₂ H—C _1-15 fluoroalkylene group or a C 1-16 perfluoroalkyl group. Moreover, Rf is particularly preferably a perfluoroalkyl group having 1 to 16 carbon atoms.

A “perfluoroalkyl group having 1 to 16 carbon atoms” may be linear or branched. The number of carbon atoms in the straight or branched chain of the "perfluoroalkyl group having 1 to 16 carbon atoms" is preferably 1 to 6, more preferably 1 to 3. The "perfluoroalkyl group having 1 to 16 carbon atoms" is particularly preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms. The “straight-chain perfluoroalkyl group having 1 to 3 carbon atoms” is specifically —CF ₃ , —CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₃ .

In formulas (1) and (2), PFPE is each independently -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

a, b, c, d, e, and f are each independently integers of 0 or more and 200 or less, and the sum of a, b, c, d, e, and f is at least 1; Each of a, b, c, d, e, and f is preferably an integer of 0 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more. Specifically, the sum of a, b, c, d, e, and f may be 10 or more and 100 or less. Moreover, the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary.

These repeating units may be linear or branched, but preferably linear. For example, - ₍ _OC6F12 )- is - ₍ _{OCF2CF2CF2CF2CF2CF2} )-, - ₍ _OCF ₍ _CF3 ₎ _CF2CF2CF2CF2 ₎ -, - ₍ _OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )- , -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, etc., but preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. - ₍ _OC5F10 )- is - ₍ _{OCF2CF2CF2CF2CF2} )-, - ₍ _OCF ₍ _CF3 ) _CF2CF2CF2 )-, - ₍ _OCF2CF ₍ _CF3 ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, but preferably -( OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )—. -( _OC4F8 )- is - ₍ _{OCF2CF2CF2CF2} )-, - ₍ OCF ₍ _CF3 ) _CF2CF2 )-, - ₍ _OCF2CF ₍ _CF3 ) _CF2 )- , -( _OCF2CF2CF ( _CF3 ))-, -(OC( _CF3 ) _2CF2 )-, -( _OCF2C _(CF3)2 ₎ _- , -(OCF ₍ _CF3 )CF( CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )-, or -(OCF ₂ CF(C ₂ F ₅ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- is any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, or -(OCF ₂ CF(CF ₃ ))- but preferably -(OCF ₂ CF ₂ CF ₂ )-. In addition, -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )- be.

In one aspect, each PFPE is independently -(OC ₃ F ₆ ) _d - (d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). Each PFPE is independently -(OCF ₂ CF ₂ CF ₂ ) _d - (d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less), or -(OCF ( CF ₃ )CF ₂ ) _d − (d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). Each PRPF is more preferably independently -(OCF ₂ CF ₂ CF ₂ ) _d - (d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). .

In another aspect, each PFPE is independently -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -. At this time, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less The order of occurrence of each repeating unit bracketed with c, d, e, or f, which is an integer, is arbitrary. Each PFPE is preferably independently -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _f - . In one aspect, each PFPE may independently be -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -. At this time, e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and each repetition bracketed with e or f The order in which the units are present is arbitrary.

In yet another aspect, each PFPE is independently a group represented by -(R ⁶ -R ⁷ ) _q -. _R6 is ^OCF2 _or _OC2F4 , _preferably _OC2F4 . ^R7 is a group selected from the _group _consisting of _OC2F4 , _OC3F6 _, _OC4F8 , _OC5F10 , and _OC6F12 , or _{independently} _selected from these groups is a combination of two or three groups that are ^R7 is a group selected from the group _consisting of _OC2F4 , _OC3F6 and _OC4F8 , or a combination of _two or _three groups independently selected from these groups is preferred. The combination of two or three groups independently selected from the group consisting of OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F _8OC4F8- _, _-OC4F8OC3F6- _, _-OC4F8OC2F4- _, _{-OC2F4OC2F4OC3F6-} _, _-OC2F4OC _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _2F4OC4F8- _, _{-OC2F4OC3F6OC2F4-} _, _{-OC2F4OC3F6OC3F6-} _, _{-OC2F4OC4F8OC2} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ -, - OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ - and the like. q is an integer of 2-100, preferably an integer of 2-50. _OC2F4 , _OC3F6 _, _OC4F8 , _OC5F10 and _OC6F12 _can be _either _linear or _branched , preferably linear. In this aspect, each PFPE is preferably independently -(OC ₂ F ₄ -OC ₃ F ₆ ) _q - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _q -.

In formulas (1) and (2), A each independently represents a functional group that selectively chemisorbs to the second region A2 of the first region A1 and the second region A2 at each occurrence, for example Represents -COOH, -SH, or -P(=O)(OH) ₂ .

In formulas (1) and (2), each X independently represents a single bond or a divalent to decavalent organic group. X is a perfluoropolyether portion (that is, Rf-PFPE portion or -PFPE- portion) that mainly provides water repellency, surface slipperiness, etc. in the compound represented by formula (1) or (2); It is understood as a linker that connects the binding portion (ie group A) that provides the ability to bind to the substrate. Therefore, X may be any organic group as long as the compound represented by formula (1) or (2) can exist stably.

In formulas (1) and (2), α is an integer of 1-9, and α' is an integer of 1-9. α and α' can vary depending on the valence of X. In formula (1), the sum of α and α' is the same as the valence of X. For example, if X is a decavalent organic group, the sum of α and α' is 10, for example, α is 9 and α' is 1, α is 5 and α' is 5, or α is 1 and α' can be 9. Also, when X is a divalent organic group, α and α' are 1. In Equation (2), α is the value obtained by subtracting 1 from the valence of X.

X is preferably a divalent to heptavalent, more preferably divalent to tetravalent, particularly preferably divalent organic group.

In one embodiment, X is a divalent to tetravalent organic group, α is 1 to 3, and α' is 1.

In another embodiment, X is a divalent organic group, α is 1, and α' is 1. In this case, the formulas (1) and (2) are represented by the following formulas (3) and (4).

In preferred embodiments of formulas (3) and (4), X is each independently, but not particularly limited to, for example, a divalent group represented by formula (5) below.

In formula (5), R ³¹ represents a single bond, —(CH ₂ ) _s′ —, or an o-, m-, or p-phenylene group, preferably —(CH ₂ ) _s′ —. s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, particularly preferably 1 or 2. X ^a represents —(X ^b ) _l′ —, and each occurrence of X ^b is independently —O—, —S—, o-, m-, or p-phenylene group, —C( O)O—, —Si(R ³³ ) ₂ —, —(Si(R ³³ ) ₂ O) _m″ —Si(R ³³ ) ₂ —, —CONR ³⁴ —, —O—CONR ³⁴ —, —NR ³⁴ represents a group selected from the group consisting of -, and -(CH ₂ ) _n' -, wherein each occurrence of R ³³ is independently at each occurrence a phenyl group, a C _1-6 alkyl group, or a C _1-6 alkoxy; group, preferably a phenyl group or a C _1-6 alkyl group, more preferably a methyl group, each occurrence of R ³⁴ is independently a hydrogen atom, a phenyl group, or a C _1-6 alkyl group; represents a group (preferably a methyl group). m″ at each occurrence is independently an integer of 1-100, preferably an integer of 1-20. n', at each occurrence, is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3. l' is an integer of 1-10, preferably an integer of 1-5, more preferably an integer of 1-3. p1 is 0 or 1; q1 is 0 or 1; At least one of p1 and q1 is 1, and the order of existence of each repeating unit enclosed in parentheses with p1 or q1 is arbitrary. R ³¹ and X ^a (typically hydrogen atoms of R ³¹ and X ^a ) are one or more selected from the group consisting of a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group may be substituted by a substituent of

Each X is preferably independently -(R ³¹ ) _p1 -(X ^a ) _q1 -R ³² -. R ³² represents a single bond, -(CH ₂ ) _t' -, or an o-, m- or p-phenylene group, preferably -(CH ₂ ) _t' -. t' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. R ³² (typically the hydrogen atom of R ³² ) is substituted with one or more substituents selected from the group consisting of a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group; good too.

Each X preferably and independently can be a C _1-20 alkylene group, —R ³¹ —X ^c —R ³² —, or —X ^d —R ³² —. In this formula, R ³¹ and R ³² have the same meanings as above.

X is more preferably each independently a C _1-20 alkylene group, —(CH ₂ ) _s′ —X ^c —, —(CH ₂ ) _s′ —X ^c —(CH ₂ ) _t′ —, —X ^d —, or —X ^d —(CH ₂ ) _t′ —. In this formula, s' and t' have the same meanings as above.

X ^c is —O—, —S—, —C(O)O—, —CONR ³⁴ —, —O—CONR ³⁴ —, —Si(R ³³ ) ₂ —, —(Si(R ³³ ) ₂ O ) _m″ —Si(R ³³ ) ₂ —, —O—(CH ₂ ) _u′ —(Si(R ³³ ) ₂ O) _m” —Si(R ³³ ) ₂ —, —O—(CH ₂ ) _{u '} -Si(R ³³ ) ₂ -O-Si(R ³³ ) ₂ -CH ₂ CH ₂ -Si(R ³³ ) ₂ -O-Si(R ³³ ) ₂ -, -O-(CH ₂ ) _u' - Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ —, —CONR ³⁴ —(CH ₂ ) _u′ —(Si(R ³³ ) ₂ O) _m″ —Si(R ³³ ) ₂ —, —CONR ³⁴ —( CH ₂ ) _u′ —N(R ³⁴ )—, or —CONR ³⁴ —(o-, m-, or p-phenylene)—Si(R ³³ ) ₂ —, where R ³³ , R ³⁴ , and m″ have the same meanings as above. u' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. X ^c is preferably -O-.

X ^d is —S—, —C(O)O—, —CONR ³⁴ —, —CONR ³⁴ —(CH ₂ ) _u′b —(Si(R ³³ ) ₂ O) _m″ —Si(R ³³ ) _2- , -CONR ³⁴ -(CH ₂ ) _u' -N(R ³⁴ )-, or -CONR ³⁴ -(o-, m-, or p-phenylene)-Si(R ³³ ) ₂ -. In the formula, each symbol has the same meaning as above.

More preferably, each X is independently a C _1-20 alkylene group, —(CH ₂ ) _s′ —X ^c —(CH ₂ ) _t′ —, or —X ^d —(CH ₂ ) _t′ — can be In this formula, each symbol has the same meaning as above.

Particularly preferably, each X is independently a C _1-20 alkylene group, —(CH ₂ ) _s′ —O—(CH ₂ ) _t′ —, —(CH ₂ ) _s′ —(Si(R ³³ ) ₂ O) _m″ —Si(R ³³ ) ₂ —(CH ₂ ) _t′ —, —(CH ₂ ) _s′ —O—(CH ₂ ) _u′ —(Si(R ³³ ) ₂ O) _m” —Si(R ³³ ) ₂ —(CH ₂ ) _t′ —, or —(CH ₂ ) _s′ —O—(CH ₂ ) _t′ —Si(R ³³ ) ₂ —(CH ₂ ) _u′ —Si( R ³³ ) ₂ -(C _v H _2v )-. R ³³ , m″, s′, t′ and u′ have the same meanings as above, v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3 .

-(C _v H _2v )- may be linear or branched, for example -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ ) -, or -CH(CH ₃ )CH ₂ -.

Each X is independently one or more substituents selected from the group consisting of a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group (preferably a C _1-3 perfluoroalkyl group) It may be substituted by a group.

In one aspect, each X may independently be other than a —O—C _1-6 alkylene group.

In another aspect, X includes, for example, groups represented by the following formulas (6) to (12).

In formulas (6) to (12), each R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group. . D is -CH ₂ O(CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ -, -CF ₂ O(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CONH-(CH ₂ ) ₃ -, -CON(CH ₃ )-(CH ₂ ) ₃ -, -CON(Ph)-(CH ₂ ) ₃ - (Ph is phenyl is a group selected from the group consisting of ) and groups represented by the following formula (13).

In formula (13), each R ⁴² is independently a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably is a methyl group.

In formulas (6) to (12), E is —(CH ₂ ) _n — (n is an integer from 2 to 6), D is attached to the PFPE of the molecular backbone, and E is opposite to PFPE. to the group of

Specific examples of X include:
—CH ₂ O(CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ —,
—CH ₂ O(CH ₂ ) ₆ —,
—CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CH ₂ OCF ₂ CHFOCF ₂ —,
—CH ₂ OCF ₂ CHFOCF ₂ CF ₂ —,
_{-CH2OCF2CHFOCF2CF2CF2-} _, _{_} _{_} _{_}
_{-CH2OCH2CF2CF2OCF2-} _, _{_} _{_} _{_}
_{-CH2OCH2CF2CF2OCF2CF2-} _, _{_} _{_} _{_} _{_}
_{-CH2OCH2CF2CF2OCF2CF2CF2-} _, _{_} _{_} _{_} _{_} _{_}
_{-CH2OCH2CF2CF2OCF} ₍ _CF3 ₎ _CF2OCF2- _, _{_}
_{-CH2OCH2CF2CF2OCF} ₍ _CF3 ₎ _CF2OCF2CF2- _, _{_} _{_}
_{-CH2OCH2CF2CF2OCF} ₍ _CF3 ₎ _{CF2OCF2CF2CF2-} _, _{_} _{_} _{_}
_{-CH2OCH2CHFCF2OCF2-} _, _{_} _{_}
_{-CH2OCH2CHFCF2OCF2CF2-} _, _{_} _{_} _{_}
_{-CH2OCH2CHFCF2OCF2CF2CF2-} _, _{_} _{_} _{_} _{_}
_{-CH2OCH2CHFCF2OCF} ₍ _CF3 ₎ _CF2OCF2- _,
_{-CH2OCH2CHFCF2OCF} ₍ _CF3 ₎ _CF2OCF2CF2- _, _{_}
_{-CH2OCH2CHFCF2OCF} ₍ _CF3 ₎ _{CF2OCF2CF2CF2-} _, _{_} _{_}
_-CH2OCH2 ( _CH2 ) _7CH2Si ₍ OCH3) _2OSi ₍ OCH3) ₂ ₍ _CH2 ) _2Si ₍ OCH3) _2OSi ₍ OCH3) ₂ ₍ _CH2 ) _2- ,
_{-CH2OCH2CH2CH2Si} ₍ OCH3) _2OSi ₍ _OCH3 ) ₂ ₍ _CH2 ) _3- _,
_{-CH2OCH2CH2CH2Si} ₍ _OCH2CH3 ) _2OSi ₍ _OCH2CH3 ) ₂ ₍ _CH2 ₎ _3- _,
_{-CH2OCH2CH2CH2Si} ₍ _OCH3 ) _2OSi ₍ _OCH3 ) ₂ ₍ _CH2 ) _2- ,
_{-CH2OCH2CH2CH2Si} ₍ _OCH2CH3 ) _2OSi ₍ _OCH2CH3 ) ₂ ₍ _CH2 ₎ _2- _,
-(CH ₂ ) ₂ -,
-(CH ₂ ) ₃ -,
-(CH ₂ ) ₄ -,
-(CH ₂ ) ₅ -,
-( _CH2 ) _6- ,
—CONH—(CH ₂ ) ₃ —,
-CON(CH ₃ )-(CH ₂ ) ₃ -,
-CON(Ph)-(CH ₂ ) ₃ - (wherein Ph means phenyl),
—CONH—(CH ₂ ) ₆ —,
-CON(CH ₃ )-(CH ₂ ) ₆ -,
-CON(Ph)-(CH ₂ ) ₆ - (wherein Ph means phenyl),
-CONH-(CH ₂ ) ₂ NH(CH ₂ ) ₃ -,
-CONH-( _CH2 ) _6NH ( _CH2 ) _3- ,
—CH ₂ O—CONH—(CH ₂ ) ₃ —,
—CH ₂ O—CONH—(CH ₂ ) ₆ —,
-S-(CH ₂ ) ₃ -,
-(CH ₂ ) ₂ S(CH ₂ ) ₃ -,
—CONH—(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH—(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH—(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH—(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH—(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—CONH—(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ —,
—C(O)O—(CH ₂ ) ₃ —,
—C(O)O—(CH ₂ ) ₆ —,
—CH ₂ —O—(CH ₂ ) ₃ —Si(CH ₃ ) ₂ —(CH ₂ ) ₂ —Si(CH ₃ ) ₂ —(CH ₂ ) ₂ —,
—CH ₂ —O—(CH ₂ ) ₃ —Si(CH ₃ ) ₂ —(CH ₂ ) ₂ —Si(CH ₃ ) ₂ —CH(CH ₃ )—,
—CH ₂ —O—(CH ₂ ) ₃ —Si(CH ₃ ) ₂ —(CH ₂ ) ₂ —Si(CH ₃ ) ₂ —(CH ₂ ) ₃ —,
—CH ₂ —O—(CH ₂ ) ₃ —Si(CH ₃ ) ₂ —(CH ₂ ) ₂ —Si(CH ₃ ) ₂ —CH(CH ₃ )—CH ₂ —,
_-OCH2- ,
—O(CH ₂ ) ₃ —,
_-OCFHCF2- ,
a group represented by the following formula (14),
a group represented by the following formula (15),
etc.

In yet another aspect, each X is independently a group represented by the following formula (16).

In formula (16), x, y, and z are each independently an integer of 0 to 10, the sum of x, y, and z is 1 or more, and each parenthesized repeating unit The order of existence is arbitrary. Each occurrence of R ¹⁶ is independently an oxygen atom, phenylene, carbazolylene, —NR ²⁶ — (R ²⁶ represents a hydrogen atom or an organic group), or a divalent organic group, preferably oxygen It is an atom or a divalent polar group.

The "divalent polar group" is not particularly limited, but -C(O)-, -C(=NR ²⁷ )-, and -C(O)NR ²⁷ - (R ²⁷ is a hydrogen atom or a lower alkyl represents a group). A "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, or n-propyl), which may be substituted with one or more fluorine atoms.

In formula (16), each occurrence of R ¹⁷ is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, preferably a fluorine atom. The number of carbon atoms in the "lower fluoroalkyl group" is, for example, 1-6. The "lower fluoroalkyl group" is preferably a fluoroalkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, particularly preferably is a trifluoromethyl group.

In yet another aspect, examples of X include groups represented by formulas (17) to (24).

In formulas (17) to (24), each R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group. .

In each X, any some of the Ts are the following groups attached to PFPE of the molecular backbone.
—CH ₂ O(CH ₂ ) ₂ —,
—CH ₂ O(CH ₂ ) ₃ —,
—CF ₂ O(CH ₂ ) ₃ —,
-(CH ₂ ) ₂ -,
-(CH ₂ ) ₃ -,
-(CH ₂ ) ₄ -,
—CONH—(CH ₂ ) ₃ —,
-CON(CH ₃ )-(CH ₂ ) ₃ -,
-CON(Ph)-(CH ₂ ) ₃ - (wherein Ph means phenyl),
Or a group represented by the following formula (25).

In formula (25), each R ⁴² is independently a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably is a methyl group.

Some of the other Ts are —(CH ₂ ) _n″ — (where n″ is an integer from 2 to 6) attached to groups opposite PFPE on the molecular backbone, and if present, the remaining Ts are Each is independently a methyl group, a phenyl group, a C _1-6 alkoxy group, a radical scavenging group, or an ultraviolet absorbing group.

The radical scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation. , hindered amines, hindered phenols, residues of triazines, and the like.

The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, and oxamides. , oxanilides, benzoxazinones, benzoxazole residues, and the like.

In preferred embodiments, preferred radical-scavenging groups or UV-absorbing groups include groups represented by the following formulas (26) to (28).

In this aspect, each X may independently be a trivalent to decavalent organic group.

The perfluoropolyether group-containing compound (reactive perfluoropolyether group-containing silane compound) used in the present embodiment has a number average molecular weight of 1,000 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 30,000. 10000.

The organic compound has, at one end of its molecular chain, a functional group that selectively chemisorbs to the second region A2 out of the first region A1 and the second region A2. The organic compound is, for example, a carboxylic acid-based compound, a thiol-based compound, or a phosphonic acid-based compound. For example, in the above formulas (1) and (2), each occurrence of A independently represents a functional group that selectively chemisorbs to the second region A2 of the first region A1 and the second region A2. for example —COOH, —SH, or —P(=O)(OH) ₂ .

Carboxylic acid-based compounds, thiol-based compounds, and phosphonic acid-based compounds are more likely to chemically adsorb to the metal film 12 than to the dielectric film 11 . Therefore, when the dielectric film 11 is exposed in the first region A1 and the metal film 12 is exposed in the second region A2, the organic film is selectively applied to the second region A2 between the first region A1 and the second region A2. A membrane 13 is formed.

In this embodiment, the first film is the dielectric film 11, the second film is the metal film 12, and the organic film 13 is selectively formed on the metal film 12 between the dielectric film 11 and the metal film 12. However, the technology of the present disclosure is not limited to this. For example, the first film may be a metal film, the second film may be a dielectric film, and the organic film 13 may be selectively formed on the dielectric film between the metal film and the dielectric film.

The organic compound contains a perfluoroether group. Organic compounds containing perfluoroether groups may be commercially available, such as Demnum (registered trademark) from Daikin Industries, Ltd., or Fomblin (registered trademark) from Ausimont. used, and those having a carboxylic acid at the end are used. Specifically, for example, Demnum carboxylic acid (DMCA) or fomblin carboxylic acid (FBCA) is used.

Demnum carboxylic acid (DMCA) is a compound represented by CF ₃ —(CF ₂ CF ₂ CF ₂ O) _n —COOH. —(CF ₂ CF ₂ CF ₂ O) _n — (n is an integer of 1 or more) is a perfluoroether group. n is 200 or less, for example.

Fomblin carboxylic acid (FBCA) is a compound represented by CF ₃ —(CF ₂ OCF ₂ CF ₂ O) _n —COOH. —(CF ₂ OCF ₂ CF ₂ O) _n — (n is an integer of 1 or more) is a perfluoroether group. n is 200 or less, for example.

A perfluoroether group has an ether group. The ether group traps the material of the first target film 14, such as an organometallic compound or a metal oxide, in step S4, which will be described later. For example, if the first target film 14 is an aluminum oxide film, it traps organoaluminum compounds or aluminum oxides.

By trapping the material of the first target film 14 inside the organic film 13, the material of the first target film 14 and the organic film 13 can be reacted. A perfluoroether group has a CF bond and produces a metal fluorocarbon by reaction with an organometallic compound or a metal oxide. The metal fluorocarbide can be vaporized at a temperature lower than the decomposition temperature of the organic film 13 and removed by evacuation.

The amount of the material of the first target film 14 trapped inside the organic film 13 can be controlled by the amount of oxygen in one molecule of the organic compound. The larger the amount of oxygen in one molecule of the organic compound, the larger the amount of traps. Among fomblin carboxylic acid and Demnum carboxylic acid having the same molecular weight, fomblin carboxylic acid has a larger amount of oxygen per molecule and a larger trap amount.

The above step S3 may include supplying a plurality of organic compounds having different compositions to the surface of the substrate 1. For example, Fomblin carboxylic acid and Demnum carboxylic acid may be applied to the surface of substrate 1 . The trap amount can be controlled by controlling the mixing ratio of a plurality of organic compounds having different compositions.

In step S4 of FIG. 1, as shown in FIG. 3C, the organic film 13 formed in the second region A2 is used to selectively form the first region A1 of the first region A1 and the second region A2. Forming a target film 14 is included. The first target film 14 is, for example, a dielectric film. A new dielectric film can be laminated on the dielectric film 11 prepared in advance.

The first target film 14 is not particularly limited, but for example, an aluminum oxide film (AlO film), a silicon oxide film (SiO film), a silicon nitride film (SiN film), a zirconium oxide film (ZrO film), or a hafnium oxide film ( HfO film) and the like. Here, the AlO film means a film containing aluminum (Al) and oxygen (O). The atomic ratio of Al and O in the AlO film is not limited to 1:1. The same is true for the SiO film, SiN film, ZrO film, and HfO film.

The method of forming the first target film 14 is, for example, physical vapor deposition, chemical vapor deposition (CVD), or atomic layer deposition (ALD). When a metal oxide is used as the material of the first target film 14, a physical vapor deposition (PVD) method is used. Physical vapor deposition methods include, for example, electron beam evaporation. On the other hand, when an organometallic compound is used as the material of the first target film 14, the CVD method or the ALD method is used.

When forming the first target film 14 by the ALD method, an organometallic compound gas and an oxidizing gas or a nitriding gas are alternately supplied to the surface of the substrate 1 . For example, when an AlO film is formed by the ALD method, an organoaluminum compound gas such as TMA (trimethylaluminum) gas and an oxidizing gas such as water vapor (H ₂ O gas) are alternately supplied to the surface of the substrate 1 . be.

The AlO film forming method includes steps S41 to S45 shown in FIG. 2, for example. First, in step S41, the surface of the substrate 1 is supplied with an organoaluminum compound gas. Next, in step S42, an inert gas such as Ar gas is supplied to the surface of the substrate 1 to purge excess organoaluminum compound gas that has not chemically adsorbed onto the surface of the substrate 1. FIG. Next, in step S43, an oxidizing gas is supplied to the surface of the substrate 1. As shown in FIG. Next, in step S44, an inert gas such as Ar gas is supplied to the surface of the substrate 1 to purge excess oxidizing gas that has not chemically adsorbed onto the surface of the substrate 1. FIG. Note that the order of steps S41 and S43 may be reversed.

Next, in step S45, it is checked whether steps S41 to S44 have been performed a set number of times. The set number of times in step S45 is set according to the target film thickness of the AlO film, and is, for example, 20 to 80 times. If the number of times of execution has not reached the set number of times (step S45, NO), steps S41 to S44 are executed again. On the other hand, if the number of times of execution has reached the set number of times (step S45, YES), the film thickness of the AlO film has reached the target film thickness, so this process is terminated.

An example of processing conditions for step S4 is shown below.
・Step S41
Flow rate of TMA gas: 50 sccm
Processing time: 0.1 sec to 2 sec
・Step S42
Ar gas flow rate: 1000 sccm to 8000 sccm
Processing time: 0.5 sec to 2 sec
・Step S43
H ₂ O gas flow rate: 50 sccm to 200 sccm
Processing time: 0.5 sec to 2 sec
・Step S44
Ar gas flow rate: 1000 sccm to 8000 sccm
Processing time: 0.5 sec to 5 sec
・Processing conditions common to steps S41 to S44 Processing temperature: 100°C to 250°C
Processing pressure: 133 Pa to 1200 Pa.

During the formation of the first target film 14, the organic film 13 inhibits the deposition of the first target film 14 while incorporating a desired amount of the material of the first target film 14 (eg, an organometallic compound). For example, the organic film 13 has hydrophobicity derived from a perfluoroether group and inhibits the chemisorption of water vapor, thereby inhibiting the deposition of the first target film 14 .

The step S4 includes reacting the organic film 13 with the material of the first target film 14 introduced into the organic film 13 to etch the organic film 13, as shown in FIG. 3C. Materials that react with the organic film 13 of the first target film 14 include organometallic compounds such as TMA, or metal oxides.

A metal fluorocarbon is generated by the reaction between the organometallic compound or the metal oxide and the perfluoroether group of the organic film 13 . The metal fluorocarbide can be vaporized at a temperature lower than the decomposition temperature of the organic film 13 and removed by evacuation.

According to this embodiment, the organic film 13 can be etched with the material of the first target film 14 and the organic film 13 can be removed. Further, according to the present embodiment, by removing the organic film 13, the material of the first target film 14 that has entered into the organic film 13 can also be removed. Therefore, the first target layer 14 can be selectively formed in the first area A1 of the first area A1 and the second area A2.

According to the present embodiment, unlike the prior art, the material of the first target film 14 is intentionally taken into the organic film 13 when the first target film 14 is formed, and the taken-in material of the first target film 14 is used. The organic film 13 is etched. Therefore, the step of supplying a dedicated etchant to the substrate 1 becomes unnecessary.

The amount of etching of the organic film 13 with the material of the first target film 14 can be controlled by the supply amount of the material of the first target film 14 , the amount of oxygen in one molecule of the organic compound, or the temperature of the substrate 1 . . For example, etching can be performed if the amount of material supplied for the first target film 14 is such that it can react with the organic film 13 at the temperature of the substrate 1 . The supply amount of the material for the first target film 14, the amount of oxygen in one molecule of the organic compound, or the temperature of the substrate 1 are appropriately controlled within the amount capable of reacting.

In this embodiment, the organic film 13 is etched with the material of the first target film 14 during the formation of the first target film 14 . More specifically, in step S41, the organic film 13 is etched with the TMA gas while the TMA gas is being supplied. The substrate 1 is heated such that the etching of the organic film 13 proceeds during the formation of the first target film 14 . The heating temperature of the substrate 1 is, for example, 100.degree. C. to 250.degree. The throughput can be improved by proceeding with the etching while supplying the TMA gas.

In this embodiment, the organic film 13 is etched with the material of the first target film 14 during the formation of the first target film 14, but after the formation of the first target film 14, the temperature of the substrate 1 is raised and the It is also possible to etch the organic film 13 with the material of the target film 14 .

In step S4, most of the organic film 13 may be removed, as shown in FIG. 3D. The organic film 13 may not remain on the surface of the substrate 1 after step S4. If the organic film 13 is removed during the formation of the first target film 14, a dedicated step for removing the organic film 13 after the formation of the first target film 14 can be omitted.

In step S5 of FIG. 1, it is checked whether steps S3 to S4 have been performed a set number of times. The set number of times in step S5 may be one, but preferably a plurality of times. That is, it is preferable to repeat a series of processes including forming the organic film 13, forming the first target film 14, and etching the organic film 13 with the material of the first target film 14. . During the formation of the first target film 14, the organic film 13 can be replenished, and the first target film 14 can be formed more selectively.

If the number of times of implementation has not reached the set number of times (step S5, NO), steps S3 and S4 are performed again. The set number of times of step S5 is set according to the final target film thickness of the AlO film. On the other hand, if the number of times of execution has reached the set number of times (step S5, YES), the film thickness of the AlO film has reached the final target film thickness, so the next step S6 is executed.

Step S6 of FIG. 1 includes forming a second target film 15 of a material different from that of the first target film 14 in the second region A2 from which the organic film 13 has been removed, as shown in FIG. 3E. The method of forming the second target film 15 is, for example, a physical vapor deposition method, a chemical vapor deposition (CVD) method, or an atomic layer deposition (ALD) method. The second target film 15 is, for example, a metal film. A new metal film can be laminated on the metal film 12 prepared in advance.

[Deposition equipment]
Next, with reference to FIG. 4, a film forming apparatus 100 for carrying out the above film forming method will be described. As shown in FIG. 4, the film forming apparatus 100 includes a first processing section 200A, a second processing section 200B, a third processing section 200C, a fourth processing section 200D, a transport section 400, and a control section 500. have 200 A of 1st process parts implement FIG.1 S2. The second processing unit 200B performs step S3 in FIG. 200 C of 3rd process parts implement FIG.1 S4. The fourth processing unit 200D implements step S6 in FIG. The first processing section 200A, the second processing section 200B, the third processing section 200C, and the fourth processing section 200D have the same structure. Therefore, it is also possible to perform all steps S2 to S4 and S6 in FIG. 1 only by the first processing unit 200A. The transport section 400 transports the substrate 1 to the first processing section 200A, the second processing section 200B, the third processing section 200C, and the fourth processing section 200D. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, and the transport unit 400. FIG.

The transport section 400 has a first transport chamber 401 and a first transport mechanism 402 . The internal atmosphere of the first transfer chamber 401 is an air atmosphere. A first transport mechanism 402 is provided inside the first transport chamber 401 . The first transport mechanism 402 includes an arm 403 that holds the substrate 1 and travels along rails 404 . The rail 404 extends in the direction in which the carriers C are arranged.

The transport section 400 also has a second transport chamber 411 and a second transport mechanism 412 . The internal atmosphere of the second transfer chamber 411 is a vacuum atmosphere. A second transport mechanism 412 is provided inside the second transport chamber 411 . The second transport mechanism 412 includes an arm 413 that holds the substrate 1, and the arm 413 is arranged movably in the vertical and horizontal directions and rotatable around the vertical axis. A first processing section 200A, a second processing section 200B, a third processing section 200C, and a fourth processing section 200D are connected to the second transfer chamber 411 through different gate valves G. FIG.

Furthermore, the transport section 400 has a load lock chamber 421 between the first transport chamber 401 and the second transport chamber 411 . The internal atmosphere of the load lock chamber 421 is switched between a vacuum atmosphere and an atmospheric atmosphere by a pressure regulating mechanism (not shown). Thereby, the inside of the second transfer chamber 411 can always be maintained in a vacuum atmosphere. In addition, the flow of gas from the first transfer chamber 401 to the second transfer chamber 411 can be suppressed. Gate valves G are provided between the first transfer chamber 401 and the load lock chamber 421 and between the second transfer chamber 411 and the load lock chamber 421 .

The control unit 500 is, for example, a computer, and has a CPU (Central Processing Unit) 501 and a storage medium 502 such as a memory. The storage medium 502 stores programs for controlling various processes executed in the film forming apparatus 100 . The control unit 500 controls the operation of the film forming apparatus 100 by causing the CPU 501 to execute programs stored in the storage medium 502 . The control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, and the transfer unit 400 to carry out the film forming method described above.

Next, the operation of the film forming apparatus 100 will be described. First, the first transport mechanism 402 takes out the substrate 1 from the carrier C, transports the taken out substrate 1 to the load lock chamber 421 , and exits from the load lock chamber 421 . Next, the internal atmosphere of the load lock chamber 421 is switched from the air atmosphere to the vacuum atmosphere. After that, the second transport mechanism 412 takes out the substrate 1 from the load lock chamber 421 and transports the taken out substrate 1 to the first processing section 200A.

Next, the first processing unit 200A performs step S2. After that, the second transport mechanism 412 takes out the substrate 1 from the first processing section 200A and transports the taken out substrate 1 to the second processing section 200B. During this time, the atmosphere around the substrate 1 can be maintained in a vacuum atmosphere, and oxidation of the substrate 1 can be suppressed.

Next, the second processing unit 200B performs step S3. After that, the second transport mechanism 412 takes out the substrate 1 from the second processing section 200B and transports the taken out substrate 1 to the third processing section 200C. During this time, the atmosphere around the substrate 1 can be maintained in a vacuum atmosphere, and the deterioration of the blocking performance of the organic film 13 can be suppressed.

Next, the third processing unit 200C performs step S4. Subsequently, the control unit 500 checks whether steps S3 to S4 have been performed a set number of times. If the number of times of execution has not reached the set number of times, steps S3 to S4 are executed again. After that, the second transport mechanism 412 takes out the substrate 1 from the third processing section 200C and transports the taken out substrate 1 to the fourth processing section 200D. During this time, the atmosphere around the substrate 1 can be maintained in a vacuum atmosphere.

Next, the fourth processing unit 200D performs step S6. After that, the second transport mechanism 412 takes out the substrate 1 from the fourth processing section 200</b>D, transports the taken out substrate 1 to the load lock chamber 421 , and exits from the load lock chamber 421 . Subsequently, the internal atmosphere of the load lock chamber 421 is switched from the vacuum atmosphere to the air atmosphere. After that, the first transport mechanism 402 takes out the substrate 1 from the load lock chamber 421 and stores the taken out substrate 1 in the carrier C. As shown in FIG. Then, the processing of the substrate 1 ends.

Next, the first processing section 200A will be described with reference to FIG. Note that the second processing unit 200B, the third processing unit 200C, and the fourth processing unit 200D are configured in the same manner as the first processing unit 200A, so illustration and description thereof will be omitted.

The first processing section 200A includes a substantially cylindrical airtight processing container 210 . An exhaust chamber 211 is provided in the central portion of the bottom wall of the processing container 210 . The exhaust chamber 211 has, for example, a substantially cylindrical shape protruding downward. An exhaust pipe 212 is connected to the exhaust chamber 211 , for example, on the side surface of the exhaust chamber 211 .

An exhaust source 272 is connected to the exhaust pipe 212 via a pressure controller 271 . The pressure controller 271 includes a pressure regulating valve such as a butterfly valve. The exhaust pipe 212 is configured such that the inside of the processing container 210 can be decompressed by the exhaust source 272 . The pressure controller 271 and the exhaust source 272 constitute a gas exhaust mechanism 270 that exhausts the gas inside the processing container 210 .

A transfer port 215 is provided on the side surface of the processing container 210 . The transfer port 215 is opened and closed by a gate valve G. Substrates 1 are carried in and out between the processing container 210 and the second transfer chamber 411 (see FIG. 4) through a transfer port 215 .

A stage 220 that is a holding portion for holding the substrate 1 is provided in the processing container 210 . The stage 220 horizontally holds the substrate 1 with the surface of the substrate 1 on which the first film and the second film are formed facing upward. The stage 220 has a substantially circular shape in plan view and is supported by a support member 221 . The surface of the stage 220 is formed with a substantially circular recess 222 for placing the substrate 1 having a diameter of 300 mm, for example. The recess 222 has an inner diameter slightly larger than the diameter of the substrate 1 . The depth of the concave portion 222 is substantially the same as the thickness of the substrate 1, for example. The stage 220 is made of a ceramic material such as aluminum nitride (AlN). Also, the stage 220 may be made of a metal material such as nickel (Ni). A guide ring for guiding the substrate 1 may be provided on the periphery of the surface of the stage 220 instead of the concave portion 222 .

A grounded lower electrode 223 is embedded in the stage 220, for example. A heating mechanism 224 is embedded under the lower electrode 223 . The heating mechanism 224 heats the substrate 1 placed on the stage 220 to a set temperature by receiving power from a power supply (not shown) based on a control signal from the control unit 500 (see FIG. 4). When the entire stage 220 is made of metal, the entire stage 220 functions as a lower electrode, so the lower electrode 223 does not have to be embedded in the stage 220 . The stage 220 is provided with a plurality of (for example, three) lifting pins 231 for holding and lifting the substrate 1 placed on the stage 220 . The material of the lifting pins 231 may be, for example, ceramics such as alumina (Al ₂ O ₃ ), quartz, or the like. A lower end of the lifting pin 231 is attached to a support plate 232 . The support plate 232 is connected to an elevating mechanism 234 provided outside the processing container 210 via an elevating shaft 233 .

The elevating mechanism 234 is installed, for example, in the lower part of the exhaust chamber 211. The bellows 235 is provided between the lifting mechanism 234 and an opening 219 for the lifting shaft 233 formed on the lower surface of the exhaust chamber 211 . The shape of the support plate 232 may be a shape that allows it to move up and down without interfering with the support member 221 of the stage 220 . The elevating pin 231 is configured to be movable between above the surface of the stage 220 and below the surface of the stage 220 by means of an elevating mechanism 234 .

A gas supply unit 240 is provided on the ceiling wall 217 of the processing container 210 via an insulating member 218 . The gas supply part 240 forms an upper electrode and faces the lower electrode 223 . A high-frequency power source 252 is connected to the gas supply unit 240 via a matching device 251 . By supplying high frequency power of 450 kHz to 100 MHz from the high frequency power supply 252 to the upper electrode (gas supply unit 240), a high frequency electric field is generated between the upper electrode (gas supply unit 240) and the lower electrode 223, and capacitively coupled plasma is generated. is generated. A plasma generator 250 that generates plasma includes a matching box 251 and a high frequency power supply 252 . The plasma generation unit 250 is not limited to capacitively coupled plasma, and may generate other plasma such as inductively coupled plasma. Note that the first processing unit 200A does not need to include the plasma generation unit 250 when the plasma processing is unnecessary.

The gas supply unit 240 has a hollow gas supply chamber 241 . A large number of holes 242 for distributing and supplying the processing gas into the processing container 210 are, for example, evenly arranged on the lower surface of the gas supply chamber 241 . A heating mechanism 243 is embedded above, for example, the gas supply chamber 241 in the gas supply unit 240 . The heating mechanism 243 is heated to a set temperature by receiving power from a power supply (not shown) based on a control signal from the controller 500 .

A gas supply mechanism 260 is connected to the gas supply chamber 241 via a gas supply path 261 . The gas supply mechanism 260 supplies the gas used in at least one of steps S2 to S4 and S6 in FIG. Although not shown, the gas supply mechanism 260 includes an individual pipe for each type of gas, an on-off valve provided in the middle of the individual pipe, and a flow controller provided in the middle of the individual pipe. When the on-off valve opens the individual pipe, gas is supplied from the supply source to the gas supply path 261 . The amount of supply is controlled by a flow controller. On the other hand, when the opening/closing valve closes the individual pipe, the supply of gas from the supply source to the gas supply path 261 is stopped.

[Experimental data]
Experimental data will be described below.

<Experimental Examples 1 and 2>
In Experimental Example 1, a substrate including a Co film having a thickness of 100 nm formed by a PVD method was prepared, the surface of the Co film was irradiated with ultraviolet rays, ozone was generated, and the ozone removed organic matter adhering to the surface of the Co film. At the same time, the oxygen density on the Co film surface was made constant.

Next, at room temperature, an organic film was formed on the surface of the Co film by PVD. Fomblin carboxylic acid (FBCA) having a molecular weight of about 4000 was prepared as an organic compound which is a material of the organic film. 50 μl of FBCA was vaporized in a crucible and evaporated onto the Co film surface at room temperature.

Next, the substrate was heated at 230°C for 30 minutes in vacuum to remove excess FBCA physically adsorbed on the Co film surface. As a result, an organic film was formed with FBCA chemically adsorbed on the Co film surface. Although the substrate was not heated during deposition of FBCA in Experimental Example 1, it may be heated.

Next, aluminum oxide (Al ₂ O ₃ ) was supplied onto the organic film by an electron beam evaporation method. The supply amount was an amount corresponding to a film thickness of 6 nm. Here, the film thickness was measured with an ellipsometer by supplying aluminum oxide on the SiO ₂ film instead of the organic film.

The temperature of the substrate was set to room temperature when aluminum oxide was supplied onto the organic film. This is to prevent the reaction between aluminum oxide and the organic film and to check the amount of aluminum oxide trapped inside the organic film.

After that, scraping the substrate surface and measuring the composition of the substrate surface by the X-ray Photoelectron Spectroscopy (XPS) method were repeated. 6A to 6C show concentration distributions of various atoms in the depth direction measured by the XPS method.

On the other hand, in Experimental Example 2, the substrate was treated in the same manner as in Experimental Example 1, except that Demnum carboxylic acid (DMCA) was prepared instead of FBCA. Thereafter, grinding the substrate surface and measuring the composition of the substrate surface by the XPS method were repeated. 6A to 6C show concentration distributions of various atoms in the depth direction measured by the XPS method.

As is clear from FIG. 6A, the concentration of C atoms decreased and the concentration of Co atoms increased until the cut depth reached D0. Further, after the depth reached D0, the concentration of C atoms became almost constant, and the concentration of Co atoms became almost constant.

From the concentration distribution of C atoms and the concentration distribution of Co atoms, it is estimated that D0 corresponds to the interface between the organic film and the Co film. The reason why the concentration of C atoms does not become zero even if the depth is deeper than D0 is due to the background of the XPS spectrum.

As is clear from FIG. 6B, between FBCA and DMCA, FBCA has a larger residual amount of aluminum oxide. This is because FBCA traps more aluminum oxide, and FBCA has more oxygen per molecule than FBCA and DMCA, which have the same molecular weight.

As is clear from FIG. 6C, between FBCA and DMCA, FBCA has a higher concentration of F atoms near the interface between the organic film and the Co film. The higher the concentration of F atoms, the easier it is for the metal fluorocarbon to volatilize.

<Experimental Examples 3 and 4>
In Experimental Example 3, when aluminum oxide was supplied onto the organic film, the temperature of the substrate was set to 230° C., the reaction between aluminum oxide and the organic film (FBCA) was promoted, and the organic film was etched. The substrate was processed as in Example 1. Thereafter, grinding the substrate surface and measuring the composition of the substrate surface by the XPS method were repeated. FIG. 7A shows the concentration distribution of various atoms in the depth direction measured by the XPS method. Further, the solid line in FIG. 7B shows the XPS spectrum when the cut depth reaches D1.

On the other hand, in Experimental Example 4, the substrate was treated in the same manner as in Experimental Example 3, except that aluminum oxide was supplied to the Co film surface without depositing FBCA on the Co film surface. After that, the substrate surface was scraped, and XPS spectra were measured when the scraped depths reached D1 and D2 (D2>D1). The XPS spectrum when the depth reaches D1 is shown by a dashed line in FIG. 7B, and the XPS spectrum when the depth reaches D2 is shown by a dashed line in FIG. 7B.

As is clear from FIG. 7A, in Experimental Example 3, until the depth reaches at least D1 (D1>D0), the concentration of Al atoms, the concentration of C atoms, the concentration of O atoms, and the concentration of F atoms Also, the concentration of Co atoms was constant. This means that in Experimental Example 3, the organic film was completely etched and an aluminum oxide film was formed on the substrate surface.

As shown by the solid line in FIG. 7B, in Experimental Example 3, a peak of Co atoms was observed when the depth reached D1. No Co atom peak was observed when the peak was reached. This indicates that the film thickness of the aluminum oxide film in Experimental Example 3 was thinner than in Experimental Example 3 and Experimental Example 4.

When the film thickness of the aluminum oxide film was actually measured with an ellipsometer, the film thickness of the aluminum oxide film in Experimental Example 3 was 2.8 nm, while the film thickness of the aluminum oxide film in Experimental Example 4 was 7.5 nm. Met. Therefore, it can be seen that the deposition of the aluminum oxide film can be restricted by forming an organic film on the surface of the Co film in advance.

As shown by the dashed line in FIG. 7B, when the depth reaches D2 (D2>D1) in Experimental Example 4, the peak of the Co atoms is the same as when the depth reaches D1 in Experimental Example 3. Admitted.

<Experimental example 5>
In Experimental Example 5, the substrate was treated in the same manner as in Experimental Example 3, except that the supply amount of aluminum oxide was reduced to an amount corresponding to a film thickness of 3 nm. Thereafter, grinding the substrate surface and measuring the composition of the substrate surface by the XPS method were repeated. FIG. 8A shows the concentration distribution of various atoms in the depth direction measured by the XPS method. Further, the XPS spectrum before grinding the substrate surface is shown by a solid line in FIG. 8B. In addition, in FIG. 8B, the dashed line indicates the XPS before the substrate surface was cut in Experimental Example 3. As shown in FIG.

As is clear from FIG. 8A, in Experimental Example 5, the concentration of C atoms and F atoms decreased and the concentration of Co atoms increased until the cut depth reached D3. Moreover, after the depth reached D3, the concentration of C atoms and F atoms became almost constant, and the concentration of Co atoms became almost constant. Therefore, in Experimental Example 5, it can be seen that an organic film having a film thickness corresponding to the depth D3 remained.

As shown by the solid line in FIG. 8B, in Experimental Example 5, a peak of C atoms due to CF bonds was observed, whereas in Experimental Example 3, as indicated by the broken line in FIG. was not accepted. This indicates that in Experimental Example 5, the amount of aluminum oxide supplied was reduced compared to Experimental Example 3, so that the organic film (FBCA) remained. Therefore, it can be seen that the etching amount of the organic film can be controlled by the supply amount of aluminum oxide.

<Experimental example 6>
In Experimental Example 6, the substrate was treated in the same manner as in Experimental Example 3, except that DMCA was used instead of FBCA as the organic compound that is the raw material of the organic film. Thereafter, grinding the substrate surface and measuring the composition of the substrate surface by the XPS method were repeated. FIG. 9 shows the concentration distribution of various atoms in the depth direction measured by the XPS method.

As is clear from FIG. 9, in Experimental Example 6, the concentration of C atoms and F atoms decreased and the concentration of Co atoms increased until the cut depth reached D4. Therefore, in Experimental Example 6, unlike Experimental Example 3, the organic film remained even after the supply of aluminum oxide. This is because between FBCA and DMCA, which have the same molecular weight, DMCA has a smaller amount of oxygen per molecule and a smaller amount of etching. Therefore, it can be seen that the etching amount of the organic film can be controlled by the amount of oxygen in one molecule.

Although the embodiments of the film forming method and film forming apparatus according to the present disclosure have been described above, the present disclosure is not limited to the above embodiments. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope of the claims. These also naturally belong to the technical scope of the present disclosure.

This application claims priority based on Japanese Patent Application No. 2021-035675 filed with the Japan Patent Office on March 5, 2021, and the entire contents of Japanese Patent Application No. 2021-035675 are incorporated into this application. .

1 substrate 1a surface 11 dielectric film (first film)
12 metal film (second film)
13 Organic film 14 First target film A1 First region A2 Second region

Claims

Preparing a substrate having on its surface a first region where a first film is exposed and a second region where a second film made of a material different from the first film is exposed;
supplying an organic compound containing a perfluoroether group to the surface of the substrate to selectively form an organic film on the second region of the first region and the second region;
selectively forming a first target film in the first region out of the first region and the second region using the organic film formed in the second region;
reacting the material of the first target film with the organic film to etch the organic film;
A film forming method, comprising:
2. The film forming method according to claim 1, wherein the organic film is etched with the material of the first target film during the formation of the first target film.
2. The film formation method according to claim 1, wherein after the formation of the first target film, the temperature of the substrate is raised and the organic film is etched with the material of the first target film.
The film forming method according to any one of claims 1 to 3, wherein forming the organic film includes supplying a plurality of the organic compounds having different compositions to the surface of the substrate.
The perfluoroether group of the organic compound is -(CF 2 CF 2 CF 2 O) n - (n is an integer of 1 or more) or -(CF 2 OCF 2 CF 2 O) n - (n is 1 or more Integer of), the film forming method according to any one of claims 1 to 4.
The film forming method according to any one of claims 1 to 5, wherein the organic compound is a carboxylic acid compound, a thiol compound, or a phosphonic acid compound.
The film forming method according to any one of claims 1 to 6, wherein the method for forming the organic film is physical vapor deposition, chemical vapor deposition, or atomic layer deposition.
The film forming method according to any one of claims 1 to 7, wherein the first film is a dielectric film and the second film is a metal film.
The film forming method according to claim 8, wherein the first target film is a dielectric film.
The film forming method according to claim 9, wherein the first target film is an aluminum oxide film, a silicon oxide film, a silicon nitride film, a zirconium oxide film, or a hafnium oxide film.
11. The film formation method according to claim 9, wherein the material to be reacted with the organic film of the first target film includes an organometallic compound or a metal oxide.
12. The film formation method according to claim 11, wherein said material to be reacted with said organic film of said first target film includes trimethylaluminum.
The film forming method according to any one of claims 1 to 12, wherein the method for forming the first target film is physical vapor deposition, chemical vapor deposition, or atomic layer deposition.
The amount of etching of the organic film with the material of the first target film is controlled by the supply amount of the material of the first target film, the amount of oxygen in one molecule of the organic compound, or the temperature of the substrate. The film forming method according to any one of claims 1 to 13, comprising:
15. The film forming method according to claim 1, further comprising forming a second target film of a material different from that of the first target film in the second region from which the organic film has been removed. .
The film forming method according to claim 15, wherein the second target film is a metal film.
3. A series of processes including forming the organic film, forming the first target film, and etching the organic film with the material of the first target film are repeatedly performed. 17. The film forming method according to any one of 1 to 16.
a processing vessel;
a holding unit that holds the substrate inside the processing container;
a gas supply mechanism for supplying gas to the inside of the processing container;
a gas discharge mechanism for discharging gas from the inside of the processing container;
a transport mechanism for loading and unloading the substrate with respect to the processing container;
a control unit that controls the gas supply mechanism, the gas discharge mechanism, and the transport mechanism, and performs the film formation method according to any one of claims 1 to 17;
A film forming apparatus.