CN116917544A - Composite structure and semiconductor manufacturing apparatus provided with composite structure - Google Patents
Composite structure and semiconductor manufacturing apparatus provided with composite structure Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000004065 semiconductor Substances 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000007373 indentation Methods 0.000 claims abstract description 18
- 210000002381 plasma Anatomy 0.000 description 50
- 238000012360 testing method Methods 0.000 description 38
- 229910052731 fluorine Inorganic materials 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000004544 sputter deposition Methods 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000000443 aerosol Substances 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001020 plasma etching Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000005524 ceramic coating Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229940105963 yttrium fluoride Drugs 0.000 description 3
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CHBIYWIUHAZZNR-UHFFFAOYSA-N [Y].FOF Chemical compound [Y].FOF CHBIYWIUHAZZNR-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
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- 238000000151 deposition Methods 0.000 description 2
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- 238000005328 electron beam physical vapour deposition Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 2
- 229940075613 gadolinium oxide Drugs 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000007541 indentation hardness test Methods 0.000 description 2
- 238000007735 ion beam assisted deposition Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
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- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
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- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
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- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- -1 shapes Substances 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
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- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- Drying Of Semiconductors (AREA)
Abstract
Disclosed are a composite structure used as a member for a semiconductor manufacturing device, which can improve the particle resistance (low-particle generation), and a semiconductor manufacturing device provided with the composite structure. The composite structure comprises: a substrate; and a structure provided on the substrate and having a surface, the structure containing Y as a main component 4 Al 2 O 9 The composite structure has excellent particle resistance, and has an indentation hardness of more than 6.0GPa, and is preferably used as a member for a semiconductor manufacturing apparatus.
Description
Technical Field
The present application relates to a composite structure excellent in particle resistance (low-particle generation) which is preferably used as a member for a semiconductor manufacturing apparatus, and a semiconductor manufacturing apparatus provided with the composite structure.
Background
There is known a technique of applying a ceramic to a surface of a substrate to impart a function to the substrate. For example, as a member for a semiconductor manufacturing apparatus used in a plasma irradiation environment such as a semiconductor manufacturing apparatus, a member having a film having high plasma resistance formed on its surface is used. For example, alumina (Al) 2 O 3 ) Yttria (Y) 2 O 3 ) Isooxide ceramics or Yttrium Fluoride (YF) 3 ) Fluoride such as Yttrium Oxyfluoride (YOF).
Furthermore, a technique has been proposed in which a protective layer is used as an oxide ceramic, and erbium oxide (Er 2 O 3 ) Or Er 3 Al 5 O 12 Gadolinium oxide (Gd) 2 O 3 ) Or Gd 3 Al 5 O 12 Yttrium aluminum garnet (YAG: Y) 3 Al 5 O 12 ) Or Y 4 Al 2 O 9 And the like (patent document 1 and patent document 2). With the miniaturization of semiconductors, various members in semiconductor manufacturing apparatuses are required to have a higher level of particle resistance.
Patent literature
Patent document 1: japanese patent application laid-open No. 2016-528380
Patent document 2: japanese patent application laid-open No. 2017-514991
Disclosure of Invention
This time, the inventors have found that yttrium and aluminum oxide Y 4 Al 2 O 9 (hereinafter, abbreviated as"yacm") as a main component, and particle resistance, which is an index of particle contamination accompanying plasma erosion, have been correlated with each other, and a structure excellent in particle resistance has been successfully produced.
Accordingly, an object of the present application is to provide a composite structure excellent in particle resistance (low-particle generation). Further, it is an object to provide a use of the composite structure as a member for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus provided with the composite structure.
The composite structure according to the present application comprises a substrate and a structure provided on the substrate and having a surface, and is characterized in that the structure contains Y as a main component 4 Al 2 O 9 And has an indentation hardness of greater than 6.0GPa.
The composite structure according to the present application is used in an environment where particle resistance is required.
The semiconductor manufacturing apparatus according to the present application includes the composite structure according to the present application.
Drawings
Fig. 1 is a schematic cross-sectional view of a member having a structure according to the present application.
Fig. 2 is a graph showing the relationship between the depth from the surface of the structure and the fluorine atom concentration after the standard plasma test 1.
Fig. 3 is a graph showing the relationship between the depth from the surface of the structure and the fluorine atom concentration after the standard plasma test 2.
Fig. 4 is an SEM image after standard plasma tests 1 and 2 of the surface of the structure.
Symbol description
10-composite structure; 15-a substrate; 20-structure; 20 a-the surface of the structure.
Detailed Description
Composite structure
The basic structure of the composite structure according to the present application will be described with reference to fig. 1. Fig. 1 is a schematic cross-sectional view of a composite structure 10 according to the present application. The composite structure 10 is composed of a structure 20 provided on a base material 15, and the structure 20 has a surface 20a.
The structure 20 of the composite structure according to the present application is a so-called ceramic coating layer. By applying ceramic coating, various physical properties and characteristics can be imparted to the base material 15. In this specification, a structure (or ceramic structure) and a ceramic coating layer are used as synonyms unless stated otherwise.
The composite structure 10 is disposed, for example, inside a chamber of a semiconductor manufacturing apparatus having a chamber. The inner wall of the cavity may also be formed by the composite structure 10. A fluorine gas such as SF or CF is introduced into the chamber to generate plasma, and the surface 20a of the structure 20 is exposed to the plasma environment. Therefore, the structure 20 located on the surface of the composite structure 10 is required to have particle resistance. The composite structure according to the present application may be used as a member that is actually installed outside the cavity. In the present specification, a semiconductor manufacturing apparatus using the composite structure according to the present application is used in a sense including any semiconductor manufacturing apparatus (semiconductor processing apparatus) that performs processes such as annealing, etching, sputtering, CVD, and the like.
Substrate material
In the present application, the substrate 15 is not particularly limited as long as it is used for its purpose, and is composed of alumina, quartz, aluminum oxide, metal, glass, or the like, preferably alumina. According to a preferred embodiment of the present application, the arithmetic average roughness Ra (Japanese Industrial Standard JISB 0601:2001) of the surface of the substrate 15 on which the structures 20 are formed is, for example, less than 5 micrometers (μm), preferably less than 1 μm, more preferably less than 0.5 μm.
Structure
In the present application, the structure contains yac as a main component. In addition, according to one aspect of the application, the YAM is polycrystalline.
In the present application, the main component of the structure means that the compound is relatively more contained than the other compounds contained in the structure 20, which is determined by quantitative or quasi-quantitative analysis based on X-ray Diffraction (XRD) of the structure. For example, the main component is the most compound contained in the structure, and the proportion of the main component in the structure is more than 50% in terms of volume ratio or mass ratio. More preferably, the proportion of the main component is more than 70%, still more preferably more than 90%. The proportion of the main component can be 100 percent.
In the present application, examples of the component that may be contained in the structure in addition to YAM include oxides such as yttrium oxide, scandium oxide, europium oxide, gadolinium oxide, erbium oxide, and ytterbium oxide, fluorides such as yttrium fluoride and yttrium oxyfluoride, and two or more of these may be contained.
In the present application, the structure is not limited to a single-layer structure, but may be a multi-layer structure. The YAM composition may also comprise multiple layers containing YAM of different compositions as main component, and other layers may be arranged between the substrate and the structure, such as Y 2 O 3 Is a layer of (c).
Indentation hardness
In the present application, the indentation hardness of the structure containing YAM as a main component is more than 6.0GPa. This can improve the particle resistance. According to a preferred embodiment of the present application, the indentation hardness is 9GPa or more, more preferably 10GPa or more, and still more preferably 11GPa or more. The upper limit of the indentation hardness is not particularly limited, and may be determined according to the required characteristics, and is, for example, 20GPa or less.
Here, the indentation hardness of the structure was measured by the following method. That is, the hardness was measured by performing a very small indentation hardness test (nanoindentation) on the surface of a structure containing YAM as a main component on a substrate. The indenter was a Mitsubishi indenter, and the indentation hardness (indentation hardness) H was measured by the indenter having a fixed value of 200nm IT . As H on the surface IT The surface other than the flaws and dents was selected. More preferably, the surface is a smooth surface on which polishing is performed. The number of measurement points is at least 25 points or more. H of 25 points or more measured IT The average value of (2) is regarded as the hardness in the present application. Other test methods and analysis methods, sequences for verifying the performance of test devices, and conditions required for standard reference samples are in accordance with ISO14577.
A fluorine-based plasma, which is a highly corrosive plasma using a CF-based gas, a SF-based gas, or the like, is used in the semiconductor manufacturing apparatus. The structure containing YAM as the main component according to the present application has little change in crystal structure even when exposed to such fluorine-based plasma and fluorinated. Thus, even when the material is used in an environment exposed to corrosive plasma, it is considered that the change in the crystal structure of the surface of the structure can be suppressed, and the generation of fewer particles can be realized.
According to one aspect of the present application, when the YAM contained in the structure is polycrystalline, its average crystallite size is, for example, less than 100nm, preferably less than 50nm, more preferably less than 30nm, and most preferably less than 20nm. Since the average crystallite size is small, particles generated by plasma can be reduced.
In the present application, the "multicrystalline" refers to a structure formed by bonding and aggregation of crystal particles. Preferably, the crystalline particles consist essentially of one constituent crystal. The diameter of the crystal particles is, for example, 5 nanometers (nm) or more.
In the present application, the crystallite size is measured, for example, by X-ray diffraction. As the average crystallite size, crystallite size can be calculated by the following scherrer equation.
D＝Kλ/(βcosθ)
Where D is the crystallite size, β is the half-peak width (unit: radian), θ is the Bragg angle (unit: rad), and λ is the wavelength of the characteristic X-rays used for XRD.
In the scherrer formula, β is calculated from β= (βobs- βstd). Beta ob is the half-width of the X-ray diffraction peak of the measurement sample, and beta std is the half-width of the X-ray diffraction peak of the standard sample. K is the Xele constant.
In YAM, the X-ray diffraction peak that can be used for calculation of crystallite size is a peak in monoclinic crystals of YAM that is close to diffraction angle 2θ=26.7°, a peak that is close to diffraction angle 2θ=29.6°, and a peak that is close to diffraction angle 2θ=30.6° and is close to diffraction angle 2θ=211.
The crystallite size can also be calculated from an image obtained by observation with a transmission electron microscope (Transmission Electron Microscope: TEM). For example, the average crystallite size may also be an average of the equivalent circle diameters of crystallites.
In the form in which YAM is polycrystalline, the interval between adjacent crystallites is preferably 0nm or more and less than 10nm. The interval between adjacent crystallites is the interval when the crystallites are closest to each other, and does not include a void composed of a plurality of crystallites. The interval between crystallites can be obtained from an image obtained by observation with a TEM.
Depth of penetration of fluorine
According to a preferred embodiment of the present application, the structure provided in the composite structure according to the present application exhibits excellent particle resistance when exposed to a specific fluorine-based plasma and the fluorine atom concentration at a predetermined depth from the surface is less than a predetermined value. The composite structure according to this aspect of the present application satisfies the fluorine atom concentration at the depth from the respective surfaces shown below after being exposed to fluorine-based plasma under the following 2 conditions. In the present application, the tests exposed to 2 fluorine-based plasmas are referred to as standard plasma tests 1 and 2, respectively.
The standard plasma tests 1 and 2 are tests performed under various conditions conceivable in the semiconductor manufacturing apparatus. The standard plasma test 1 envisages test conditions under which a bias power is applied, and the structure is used as a member such as a focus ring located around the wafer in the chamber, and is exposed to a corrosive environment due to radical and ion collisions. In Standard plasma test 1, the SF was evaluated 6 Performance of the plasma. On the other hand, the standard plasma test 2 assumes a test condition in which the structure is used as a sidewall member located substantially perpendicular to the silicon wafer or a ceiling member facing the silicon wafer in the chamber without applying bias power, and is less likely to collide with ions and exposed to a corrosive environment mainly due to radicals. According to a preferred embodiment of the present application, the composite structure according to the present application satisfies at least a predetermined value of the fluorine concentration in any of these tests.
(1) Plasma exposure conditions
As for the structure containing YAM as a main component on the substrate, an inductively coupled reactive ion etching (ICP-RIE) apparatus was used to expose the surface thereof to a plasma environment. The formation conditions of the plasma atmosphere were the following 2 conditions.
Standard plasma test 1:
SF of 100sccm as the process gas 6 The coil output for ICP as the power supply output was 1500W and the bias output was 750W.
Standard plasma test 2:
SF of 100sccm as the process gas 6 The coil output for ICP is set to 1500W as the power supply output, and the bias output is set to OFF (0W)). That is, high-frequency power for biasing the electrostatic chuck is not applied.
In the standard plasma tests 1 and 2, the chamber pressure was set to 0.5Pa and the plasma exposure time was set to 1 hour. The semiconductor manufacturing apparatus member is disposed on a silicon wafer adsorbed by an electrostatic chuck provided in the inductively coupled reactive ion etching apparatus so that the surface of the structure is exposed to a plasma environment formed by the conditions.
(2) Method for measuring fluorine atom concentration in depth direction on surface of structure
The atomic concentration (%) of fluorine (F) atoms at the sputtering time was measured by performing depth direction analysis by ion sputtering on the surface of the structure after the standard plasma tests 1 to 2 by X-ray photoelectron spectroscopy (XPS). Next, in order to convert the sputtering time into depth, the step(s) between the sputtered portion and the portion not sputtered by the ion sputtering was measured by a stylus surface shape measuring device. The depth (e) for a unit sputtering time was calculated from the step(s) and the total sputtering time (t) for XPS measurement, and the sputtering time was converted into the depth from the depth (e) for the unit sputtering time. Finally, the depth from the surface 20a and the fluorine (F) atom concentration (%) at the depth position were calculated.
In this embodiment, the composite structure according to the present application satisfies the fluorine atom concentration at the depth from the surface shown below after the standard plasma tests 1 and 2.
After standard plasma test 1:
fluorine atom concentration F1 at a depth of 10nm from the surface 10nm Less than 3.0%, more preferably F1 10nm F1 is more preferably 1.5% or less 10nm Is less than 1.0%.
After standard plasma test 2:
fluorine atom concentration F3 at a depth of 10nm from the surface 10nm Less than 3.0%, more preferably F3 10nm F3 is more preferably 1.0% or less 10nm Is less than 0.5%.
Manufacture of composite structures
The composite structure according to the present application can be produced by various production methods according to the purpose, as long as the structure having the lattice constant can be realized on the substrate. That is, Y is contained as a main component on the base material 4 Al 2 O 9 The substrate may be manufactured by a method capable of forming a structure having the above-described lattice constant, for example, by physical vapor deposition (PVD method) or chemical vapor deposition (CVD method). Examples of the PVD method include electron beam physical vapor deposition (EB-PVD), ion beam assisted deposition (IAD), electron beam ion assisted deposition (EB-IAD), ion plating, and sputtering. Examples of the CVD method include thermal Chemical Vapor Deposition (CVD), plasma Enhanced Chemical Vapor Deposition (PECVD), metal Organic Chemical Vapor Deposition (MOCVD), mist Chemical Vapor Deposition (CVD), laser Chemical Vapor Deposition (CVD), and Atomic Layer Deposition (ALD). In another aspect of the present application, fine particles of a brittle material or the like are disposed on the surface of the base material, and a mechanical impact force is applied to the fine particles. Here, the method of applying the mechanical impact force may be, for example, a method using a high-hardness brush or roller rotating at a high speed, a piston moving up and down at a high speed, or the like, a method using a compressive force by a shock wave generated at the time of explosion, a method using an action of ultrasonic waves, or a method using a combination of these.
The composite structure according to the present application can be preferably formed by an aerosol deposition method (AD method). The "AD method" is a method in which a "aerosol" in which fine particles containing a brittle material such as ceramic are dispersed in a gas is sprayed from a nozzle onto a substrate to cause the fine particles to collide with the substrate such as metal, glass, ceramic, or plastic at a high speed, and the fine particles of the brittle material are deformed or broken by the impact of the collision, whereby these are bonded to each other, and a structure (ceramic coating layer) of a constituent material containing the fine particles is directly formed on the substrate as a layered structure or a film-like structure, for example. According to this method, a structure can be formed at normal temperature without requiring a heating means, a cooling means, or the like, and a structure having mechanical strength equal to or higher than that of the fired body can be obtained. In addition, by controlling collision conditions of the particles, shapes, compositions, and the like of the particles, various deformations such as density, mechanical strength, electrical characteristics, and the like of the structure can be made. In order to realize the composite structure according to the present application, the conditions described below are set so as to satisfy the indentation hardness, whereby the composite structure according to the present application can be produced.
When the primary particles are dense particles, the term "fine particles" in the present specification means particles having an average particle diameter of 5 micrometers (μm) or less which tend to be equivalent under observation by a particle size distribution measurement or a scanning electron microscope or the like. When the primary particles are porous particles which are easily broken by impact, the primary particles are particles having an average particle diameter of 50 μm or less.
In the present specification, the term "aerosol" refers to a solid-gas mixed phase in which the fine particles are dispersed in a gas (carrier gas) such as helium, nitrogen, argon, oxygen, dry air, or a mixed gas containing these, and it is preferable to refer to a state in which the fine particles are substantially individually dispersed, although the term "aggregate" is also included. The gas pressure and temperature of the aerosol may be arbitrarily set in consideration of the physical properties of the desired structure, etc., but when the gas pressure is converted to 1 atmosphere and the temperature is converted to 20 degrees celsius, the concentration of the fine particles in the gas is preferably in the range of 0.0003mL/L to 5mL/L at the time of ejection from the ejection port.
In general, the aerosol deposition process is performed at normal temperature, and the structure can be formed at a temperature sufficiently lower than the melting point of the particulate material, that is, several hundred degrees celsius or less. In the present application, the term "normal temperature" means a temperature significantly lower than the sintering temperature of ceramic, and substantially means a room temperature environment of 0 to 100 ℃. In the present specification, the term "powder" refers to a state in which the fine particles naturally agglomerate.
Examples
The present application is further illustrated by the following examples, but the present application is not limited to these examples.
As the raw materials of the structures used in the examples, raw materials shown in the following table were prepared.
TABLE 1
In the table, the median diameter (D50 (μm)) means a diameter of 50% in the cumulative distribution of particle diameters of the respective raw materials. The diameter of each particle was determined by an approximate circle.
By changing the combination of these materials and the film forming conditions (the type and flow rate of the carrier gas, etc.), a plurality of samples having a structure on the substrate were produced. Regarding the obtained samples, the particle resistance after the standard plasma tests 1 to 2 was evaluated. In this example, an aerosol deposition method was used for the production of the sample.
TABLE 2
As shown in the table, nitrogen (N) 2 ) Or helium (He). An aerosol is obtained by mixing a carrier gas and a raw material powder (raw material fine particles) in an aerosol generator. The aerosol thus obtained is ejected from a nozzle connected to an aerosol generator by a pressure difference to a substrate disposed in a film forming chamber. At this time, the air in the film forming chamber is discharged to the outside by the vacuum pump.
Sample of
The structures of samples 1 to 5 thus obtained each contained YAM as a main component, and the average crystallite size in the polycrystal was less than 30nm.
XRD was used for measurement of the crystallite size. That is, "X' PertPRO/panaco" was used as the XRD device. As the measurement conditions of XRD, the characteristic X-ray is CuK alphaThe tube voltage is 45kV, the tube current is 40mA, the step length is 0.0084 DEG, and the residence time is more than 80 seconds. As the average crystallite size, crystallite size was calculated by the scherrer equation. As the K value in the scherrer formula, 0.94 is used.
The principal component of the YAM crystalline phase on the substrate was determined by XRD. As XRD device, "X' PertPRO/panaco system was used. As the measurement conditions of XRD, the characteristic X-ray is CuK alphaThe tube voltage is 45kV, the tube current is 40mA, the step length is 0.0084 DEG, and the residence time is more than 80 seconds. The main component was calculated using XRD analysis software "High Score Plus/panaceae". The relative intensity ratio required to peak the diffraction peak was calculated using the reference intensity ratio (rir= Reference Intensity Ratio) described in the ICDD card. In the case of the layered structure, it is preferable to use the measurement result in a depth region of less than 1 μm from the outermost surface by thin film XRD in the measurement of the principal component of YAM polycrystal.
Standard plasma test
In addition, regarding these samples 1 to 5, standard plasma tests 1 and 2 under the above conditions were performed, and the particle resistance after the tests were evaluated in the following order. The ICP-RIE apparatus used "Muc-21 Rv-Aps-Se/Sumitomo precision industries, ltd.). In the standard plasma tests 1 and 2, the chamber pressure was set to 0.5Pa and the plasma exposure time was set to 1 hour. The sample is placed on a silicon wafer adsorbed by an electrostatic chuck provided in an inductively coupled reactive ion etching apparatus so that the surface of the sample is exposed to a plasma environment formed by the conditions.
Measurement of indentation hardness
The indentation hardness of the structure on the substrate was evaluated by the extremely small indentation hardness test (nanoindentation) in the following order. As a very small indentation hardness tester (nanoindenter), "ENT-2100/Elionix" was used. As a condition for the extremely small press-in hardness test, a mitsubishi press-in head was used, and the test mode was a press-in depth setting test, and the press-in depth was 200nm. For indentation hardness (press-in hardness) H IT The measurement was performed. H is randomly set on the surface of the structure IT The number of measurement points is at least 25 points. H of 25 points or more measured IT The average value of (2) was used as the hardness. The results are shown in Table 2.
Determination of depth of invasion of fluorine
Regarding the surfaces of the samples after the standard plasma tests 1 and 2, the atomic concentration (%) of fluorine (F) atoms for the sputtering time was determined by performing depth direction analysis by X-ray photoelectron spectroscopy (XPS) using ion sputtering. As the XPS device, "K-Alpha/Sieimer Feishmania technology Co., ltd.) was used. Next, in order to convert the sputtering time into depth, the step(s) between the sputtered portion and the portion not sputtered by the ion sputtering was measured by a stylus surface shape measuring device. The depth (e) for a unit sputtering time was calculated from the step(s) and the total sputtering time (t) for XPS measurement, and the sputtering time was converted into the depth from the depth (e) for the unit sputtering time. Finally, the depth from the surface of the sample and the fluorine (F) atom concentration (%) at the depth position were calculated.
The depths and fluorine atom concentrations from the structure surface after standard plasma tests 1 and 2 are shown in the following table.
After standard plasma test 1:
TABLE 3 Table 3
After standard plasma test 2:
TABLE 4 Table 4
If the data is represented as a graph, it is shown in fig. 2 and 3.
SEM image
SEM images of the surfaces of the structures after standard plasma tests 1 and 2 were taken as follows. That is, the corrosion state of the plasma-exposed surface was evaluated by using a scanning electron microscope (Sccaning Electron Microscope; SEM). SEM was used "SU-8220/manufactured by Hitachi Co., ltd.). The acceleration voltage was set to 3kV. A photograph of the result is shown in FIG. 4.
Surface roughness (arithmetic mean height Sa)
Regarding the surface roughness of the structure after the standard plasma test 1, sa (arithmetic mean height) specified by ISO25178 was evaluated using a laser microscope. The laser microscope used "OLS 4500/Olympic Bassystem". The objective lens was set to a cut-off value λc of 25 μm using a mplpon 100 XLEXT. The results are shown in the following table.
TABLE 5
Evaluation of results
In view of the above results, in table 2, the case where the influence of plasma etching was small in any one of the standard plasma tests 1 and 2 was evaluated as "excellent", the case where the influence of plasma etching was small in any one of the standard plasma tests 1 and 2 was evaluated as "good", and the case where the influence of plasma etching was present under any one of the standard plasma tests 1 and 2 was evaluated as "x".
The embodiments of the present application have been described above. However, the present application is not limited to the above. The foregoing embodiments are also within the scope of the present application, as long as they have the features of the present application, and those skilled in the art can appropriately modify the design. For example, the shape, size, material, arrangement, and the like of the structure, the base material, and the like are not limited to those exemplified, and may be appropriately changed. The elements of the embodiments described above may be combined as long as the technology is technically feasible, and the combination of these techniques is also included in the scope of the present application as long as the features of the present application are included.
Claims (8)
1. A composite structure comprising a substrate and a structure having a surface and disposed on the substrate, characterized in that,
the structure contains Y as a main component 4 Al 2 O 9 And has an indentation hardness of greater than 6.0GPa.
2. The composite structure according to claim 1, wherein the indentation hardness is 9.0GPa or more.
3. The composite structure according to claim 1, wherein the indentation hardness is 10GPa or more.
4. The composite structure according to claim 1, wherein the indentation hardness is 11GPa or more.
5. A composite structure according to any one of claims 1 to 3, wherein the average crystallite size of the structure is less than 50nm.
6. The composite structure according to any one of claims 1 to 5, which is used in an environment where particle resistance is required.
7. The composite structure according to claim 6, which is a member for a semiconductor manufacturing apparatus.
8. A semiconductor manufacturing apparatus comprising the composite structure according to any one of claims 1 to 5.
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| JP2021-055621 | 2021-03-29 | ||
| JP2021-156217 | 2021-09-25 | ||
| JP2022-017677 | 2022-02-08 | ||
| JP2022017677A JP2022153274A (en) | 2021-03-29 | 2022-02-08 | Composite structure and semiconductor manufacturing apparatus including composite structure |
| PCT/JP2022/012151 WO2022209934A1 (en) | 2021-03-29 | 2022-03-17 | Composite structure, and semiconductor manufacturing device including composite structure |
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