阅读说明：本技术 复合结构物以及具备复合结构物的半导体制造装置 (Composite structure and semiconductor manufacturing apparatus provided with composite structure ) 是由 芹泽宏明 滝沢亮人 于 2021-04-30 设计创作，主要内容包括：本发明的目的在于提供一种作为可提高抗粒子性(low-particle generation)的半导体制造装置用构件而加以使用的复合结构物以及具备其的半导体制造装置。具体而言,是包含基材和设置在所述基材上且具有表面的结构物的复合结构物,所述结构物作为主成分而含有Y-(3)Al-(5)O-(12),而且其压痕硬度大于8.5GPa的复合结构物的抗粒子性比较出色,作为半导体制造装置用构件而优选被使用。(The purpose of the present invention is to provide a member for a semiconductor manufacturing apparatus, which can be used as a member for improving particle resistance (low-particle generation)And a semiconductor manufacturing apparatus provided with the same. Specifically, the composite structure comprises a substrate and a structure provided on the substrate and having a surface, wherein the structure contains Y as a main component 3 Al 5 O 12 Further, the composite structure having an indentation hardness of more than 8.5GPa is excellent in particle resistance, and is preferably used as a member for a semiconductor manufacturing apparatus.)

1. A composite structure comprising a substrate and a structure provided on said substrate and having a surface, characterized in that,

the structure contains Y as a main component₃Al₅O₁₂And the indentation hardness is more than 8.5 GPa.

2. The composite structure according to claim 1, wherein the indentation hardness is 10GPa or more.

3. The composite structure according to claim 1, wherein the indentation hardness is 13GPa or more.

4. The composite structure according to claim 1, wherein the indentation hardness is 20GPa or less.

5. A composite structure according to any of claims 1 to 4, wherein the average crystallite size of the structure is less than 50 nm.

6. A composite structure according to any one of claims 1 to 5, wherein, after standard plasma test 1, fluorine atoms at a depth of 30nm from the surface of the structure are satisfiedConcentration F1_30nmF1 fluorine atom concentration of less than 3% or at a depth of 20nm from the surface_20nmLess than 4% of at least any one of them.

7. Composite structure according to claim 6, characterized in that said fluorine atom concentration F1_30nmOr the fluorine atom concentration F1_20nmAt least any one of (a) is 2% or less.

8. A composite structure according to any one of claims 1 to 5, characterized in that after standard plasma test 2 the fluorine atom concentration F2 at a depth of 30nm from the surface of the structure is satisfied_30nmF2 concentration of fluorine atoms less than 2% or at a depth of 15nm from the surface_15nmLess than 3% of any one of them.

9. The composite structure according to claim 8, wherein said fluorine atom concentration F2 is satisfied_30nmIs 1% or less or the fluorine atom concentration F2_15nmAt least one of the amounts is 2% or less.

10. A composite structure according to any one of claims 1 to 5, characterized in that after standard plasma test 3 the fluorine atom concentration F3 at a depth of 20nm from the surface of the structure is satisfied_20nmF3 concentration of fluorine atoms less than 8% or at a depth of 10nm from the surface_10nmLess than 9% of any of the plurality of particles.

11. The composite structure according to claim 10, wherein said fluorine atom concentration F3 is satisfied_20nmIs 7% or less or the fluorine atom concentration F3_10nmAt least one of the amounts is 8% or less.

12. The composite structure according to claim 10, wherein said fluorine atom concentration F3 is satisfied_20nmIs 1% or less or the fluorine atom concentration F3_10nmIs at least 2% or lessEither one of them.

13. The composite structure according to any one of claims 1 to 12, which is used in an environment where particle resistance is required.

14. The composite structure according to claim 13, which is a member for a semiconductor manufacturing apparatus.

15. A semiconductor manufacturing apparatus comprising the composite structure according to any one of claims 1 to 12.

Technical Field

The present invention 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 including the same.

Background

A technique of applying a ceramic to a surface of a substrate to impart a function to the substrate is known. 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 coating film with high plasma resistance formed on a surface thereof is used. For example, alumina (Al) is used as the coating₂O₃) Yttrium oxide (Y)₂O₃) Oxide-based ceramics or Yttrium Fluoride (YF)₃) And fluoride ceramics such as Yttrium Oxyfluoride (YOF).

Further, a technique of using a protective layer using erbium oxide (Er) as an oxide ceramic has been proposed₂O₃) Or Er₃Al₅O₁₂Gadolinium oxide (Gd)₂O₃) Or Gd₃Al₅O₁₂Yttrium aluminum garnet (YAG: Y)₃Al₅O₁₂) Or Y₄Al₂O₉And the like (patent document 1). With the miniaturization of semiconductors, higher levels of particle resistance are required for various members in semiconductor manufacturing apparatuses.

Patent document

Patent document 1: japanese patent application laid-open No. 2016-528380

Disclosure of Invention

This time, the present inventors have found that Y is an oxide of yttrium and aluminum₃Al₅O₁₂A structure containing YAG as a main component (hereinafter abbreviated as "YAG") has a correlation between the hardness and the particle resistance, which is an index of particle contamination caused by plasma corrosion, and a structure having excellent particle resistance has been successfully produced.

Accordingly, an object of the present invention is to provide a composite structure having excellent particle resistance (low-particle generation). Further, it is an object of the present invention to provide a use of the composite structure as a member for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus using the same.

The composite structure according to the present invention comprises a base material and a structure provided on the base material and having a surface, wherein the structure contains Y as a main component₃Al₅O₁₂And the indentation hardness is more than 8.5 GPa.

The composite structure according to the present invention is used in an environment where particle resistance is required.

The semiconductor manufacturing apparatus according to the present invention includes the composite structure according to the present invention.

Drawings

Fig. 1 is a schematic sectional view of a member having a structure according to the present invention.

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 a graph showing the relationship between the depth from the surface of the structure and the fluorine atom concentration after the standard plasma test 3.

FIG. 5 is an SEM image of the surface of a structure after standard plasma tests 1-3.

Description of the symbols

10-a composite structure; 15-a substrate; 20-a structure; 20 a-the surface of the structure.

Detailed Description

Composite structure

The basic structure of the composite structure according to the present invention 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 invention. Composite structure 10 is formed of structure 20 disposed on substrate 15, structure 20 having a surface 20 a.

The structure 20 included in the composite structure according to the present invention is a so-called ceramic coating layer. By applying the ceramic coating, various physical properties and characteristics can be imparted to the substrate 15. In the present specification, the structure (or ceramic structure) and the ceramic coating layer are used synonymously unless otherwise stated.

The composite structure 10 is disposed inside a cavity of a semiconductor manufacturing apparatus having the cavity, for example. A fluorine-based gas such as SF-based or CF-based gas is introduced into the chamber to generate plasma, and the surface 20a of the structure 20 is exposed to the plasma atmosphere. Accordingly, particle resistance is required for the structure 20 located on the surface of the composite structure 10. The composite structure according to the present invention can be used as a member actually attached to the inside of a cavity. In the present specification, a semiconductor manufacturing apparatus using the composite structure according to the present invention is used in a meaning including any semiconductor manufacturing apparatus (semiconductor processing apparatus) that performs a process such as annealing, etching, sputtering, CVD, or the like.

Base material

In the present invention, the base material 15 is not particularly limited as long as it is used for its purpose, and is configured to contain alumina, quartz, alumite, metal, glass, or the like, and is preferably configured to contain alumina. According to a preferred embodiment of the present invention, the arithmetic average roughness Ra of the surface of the substrate 15 on which the structure 20 is formed (Japanese Industrial Standard JISB 0601: 2001) is, for example, less than 5 micrometers (μm), preferably less than 1 μm, and more preferably less than 0.5 μm.

Structure object

In the present invention, the structure contains YAG as a main component. In addition, according to one aspect of the present invention, YAG is polycrystalline.

In the present invention, the main component of the structure means a compound that is relatively more contained than other compounds contained in the structure 20 as determined by quantitative or quasi-quantitative analysis based on X-ray Diffraction (XRD) of the structure. For example, the main component is a compound that is contained most in the structure, and the proportion of the main component in the structure is more than 50% by volume or mass. 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 also be 100%.

In the present invention, the YAG-based constituent may contain an oxide such as yttrium oxide, scandium oxide, europium oxide, gadolinium oxide, erbium oxide, and ytterbium oxide, a fluoride such as yttrium fluoride and yttrium oxyfluoride, or two or more of these may be contained.

In the present invention, the structure is not limited to a single-layer structure, but may be a multi-layer structure. It may further comprise a plurality of layers containing YAG of different compositions as a main component, and further another layer, for example, containing Y, may be provided between the substrate and the structure₂O₃Of (2) a layer of (a).

Hardness of indentation

In the present invention, the indentation hardness of a structure containing YAG as a main component is greater than 8.5 GPa. This can improve particle resistance. According to a preferred embodiment of the present invention, the indentation hardness is 10GPa or more, more preferably 13GPa 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 YAG as a main component on a base material. The indenter was a rhomboid indenter, and the indentation depth was a fixed value of 200nm, whereby indentation hardness (indentation hardness) H was measured_IT. As H on the surface_ITThe surface of the measurement site (2) is selected except for the surface of the flaw or indentation. More preferably, the surface is a smooth surface on which grinding is performed. The number of measurement points is at least 25 points or more. More than 25 points of H are measured_ITThe average value of (2) is defined as the hardness in the present invention. Other test methods and analysis methods, the order for verifying the performance of the test apparatus, and the requirements for the standard reference sample were in accordance with ISO 14577.

Fluorine-based plasma, which is highly corrosive plasma using a CF-based gas, an SF-based gas, or the like, is used in a semiconductor manufacturing apparatus. The structure containing YAG as a main component according to the present invention has a small change in crystal structure even when exposed to such fluorine-based plasma and fluorinated. Therefore, it is considered that even when the structure is used while being exposed to an environment of corrosive plasma, the crystal structure of the structure surface can be suppressed from changing, and the generation of particles can be reduced.

According to one embodiment of the present invention, when the YAG crystal contained in the structure is polycrystalline, the average crystallite size is, for example, less than 100nm, preferably less than 50nm, more preferably less than 30nm, and most preferably less than 20 nm. Since the average crystallite size is small, the particles generated by the plasma can be reduced.

In the present specification, "polycrystalline body" refers to a structure in which crystal particles are joined and aggregated. Preferably, the crystal particles consist essentially of one constituent crystal. The diameter of the crystal particles is, for example, 5 nanometers (nm) or more.

In the present invention, the crystallite size is measured, for example, by X-ray diffraction. As the average crystallite size, the crystallite size can be calculated by the scherrer equation below.

D＝Kλ/(βcosθ)

Here, D is the crystallite size, β is the half-peak width (unit: radian (rad)), θ is the bragg angle (unit: rad), and λ is the wavelength of the characteristic X-ray used for XRD.

In the scherrer equation, β is calculated from β ═ β obs- β std. β obs is the half width of the X-ray diffraction peak of the measurement sample, and β std is the half width of the X-ray diffraction peak of the standard sample. K is the scherrer constant.

In YAG, the X-ray diffraction peak value usable for the calculation of the crystallite size is a peak value in the vicinity of 17.9 ° for the diffraction angle 2 θ ascribed to the miller index (hkl) ═ 211, a peak value in the vicinity of 27.6 ° for the diffraction angle 2 θ ascribed to the miller index (hkl) ═ 321, a peak value in the vicinity of 29.5 ° for the diffraction angle 2 θ ascribed to the miller index (hkl) ═ 400, a peak value in the vicinity of 33.1 ° for the diffraction angle 2 θ ascribed to the miller index (hkl) ═ 420, or the like in the cubic crystal of YAG.

The crystallite size can also be calculated from an image observed with a Transmission Electron Microscope (TEM). For example, the average crystallite size may also be taken as the average of the equivalent circular diameters of the crystallites.

In the case where YAG is polycrystalline, the distance between adjacent crystallites is preferably 0nm or more and less than 10 nm. The interval between adjacent crystallites is the interval when the crystallites are closest to each other, and does not include voids composed of a plurality of crystallites. The interval between crystallites can be determined from an image observed by TEM.

Depth of penetration of fluorine

According to a preferred embodiment of the present invention, the composite structure according to the present invention has a structure which exhibits, when exposed to a specific fluorine-based plasma, a particle resistance that is preferable when the fluorine atom concentration at a predetermined depth from the surface is less than a predetermined value. The composite structure according to this embodiment of the present invention satisfies the following predetermined values of the fluorine atom concentration at the depth from the surface after being exposed to the fluorine-based plasma under the following 3 conditions. In the present invention, the tests of exposure to the fluorine-based plasma under 3 conditions are referred to as standard plasma tests 1 to 3, respectively.

The standard plasma tests 1 to 3 are tests performed assuming various conditions that can be assumed in the semiconductor manufacturing apparatus. The standard plasma tests 1 and 2 assume test conditions under which bias power is applied, and the structure is used as a member such as a focus ring located around the silicon wafer inside the chamber and exposed to an etching environment due to collision of radicals and ions. In Standard plasma test 1, CHF was evaluated₃Plasma Performance in Standard plasma test 2, SF was evaluated₆The properties of the plasma. On the other hand, the standard plasma test 3 assumes test conditions under which a structure is used as a side wall member located substantially perpendicular to a silicon wafer or a top plate member facing the silicon wafer inside a chamber without applying a bias power, and is exposed to an etching environment mainly caused by radicals with less ion collisions. According to a preferred embodiment of the present invention, the composite structure according to the present invention satisfies at least the predetermined value of the fluorine concentration in any of these tests.

(1) Plasma exposure conditions

A structure containing YAG as a main component on a base material is exposed to a plasma atmosphere on the surface thereof using an inductively coupled reactive ion etching (ICP-RIE) apparatus. The formation conditions of the plasma atmosphere were the following 3 conditions.

Standard plasma test 1:

CHF made at 100sccm as a process gas₃And O of 10sccm₂The 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 a process gas₆The coil output for ICP as the power supply output was 1500W and the bias output was 750W.

Standard plasma test 3:

SF of 100sccm as a process gas₆The coil output for ICP as the power supply output is 1500W, and the bias output is OFF (0W)). That is, the high-frequency power for biasing the electrostatic chuck is not applied.

In the standard plasma tests 1-3, the cavity pressure was set to 0.5Pa and the plasma exposure time was set to 1 hour. The member for a semiconductor manufacturing apparatus is disposed on a silicon wafer which is attracted to an electrostatic chuck provided in the inductively coupled reactive ion etching apparatus so that the surface of the structure is exposed to a plasma atmosphere formed under the above conditions.

(2) Method for measuring fluorine atom concentration on structure surface in depth direction

The surface of the structure after the standard plasma tests 1 to 3 was analyzed in the depth direction by X-ray photoelectron spectroscopy (XPS) using an ion beam, and the atomic concentration (%) of fluorine (F) atoms with respect to the sputtering time was measured. Next, in order to convert the sputtering time into depth, the step(s) between the portion sputtered by the ion beam and the portion not sputtered was measured by a stylus type surface shape measuring instrument. The depth (e) per unit sputtering time is calculated from e ═ s/t by the total sputtering time (t) used for the step(s) and XPS measurements, and the sputtering time is converted into the depth by the depth (e) per 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 invention satisfies the following fluorine atom concentrations at the depths from the respective surfaces after the standard plasma tests 1 to 3.

After standard plasma test 1:

satisfying the fluorine atom concentration F1 at a depth of 30nm from the surface_30nmF1 concentration of fluorine atoms less than 3% or at a depth of 20nm from the surface_20nmLess than 4% of at least any one of them. More preferably F1_30nmOr F1_20nmAt least any one of (a) is 2% or less.

After standard plasma test 2:

satisfying the fluorine atom concentration F2 at a depth of 30nm from the surface_30nmF2 concentration of fluorine atoms less than 2% or at a depth of 15nm from the surface_15nmLess than 3% of any one of them. More preferably F2_30nmIs 1% or less or F2_15nmAt least one of the amounts is 2% or less.

After standard plasma test 3:

satisfying the fluorine atom concentration F3 at a depth of 20nm from the surface_20nmF3 concentration of fluorine atoms less than 8% or at a depth of 10nm from the surface_10nmLess than 9% of any of the plurality of particles. More preferably F3_20nmIs 7% or less or F3_10nmAt least one of the amounts is 8% or less. More preferably F3_20nmIs 1% or less or F3_10nmAt least one of the amounts is 2% or less.

Manufacture of composite structures

The composite structure according to the present invention can be formed, for example, by disposing fine particles of a brittle material or the like on the surface of a base material and applying a mechanical impact force to the fine particles. Here, as the method of "applying mechanical impact force", there may be mentioned 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, utilizing a compressive force generated by a shock wave generated at the time of explosion, utilizing the action of ultrasonic waves, or a combination thereof.

In addition, the composite structure according to the present invention can be preferably formed by an aerosol deposition method. The "aerosol deposition method" is a method in which an "aerosol" in which fine particles containing a brittle material or the like are dispersed in a gas is ejected from a nozzle toward a substrate, the fine particles collide with the substrate such as metal, glass, ceramic, or plastic, and the impact of the collision deforms or fractures the fine particles of the brittle material, thereby bonding these particles to form a structure of a constituent material containing the fine particles directly on the substrate, for example, as a layered structure or a film-like structure. According to this method, a structure can be formed at normal temperature without particularly requiring a heating means, a cooling means, or the like, and a structure having mechanical strength equal to or higher than that of a fired body can be obtained. In addition, by controlling the collision conditions of the fine particles, the shapes and the compositions of the fine particles, various deformations such as the density, the mechanical strength, and the electrical characteristics of the structure can be performed.

When the primary particles are dense particles, the term "fine particles" as used herein refers to particles having an average particle diameter of 5 micrometers (μm) or less, which is equivalent to a particle size distribution measurement or an observation by a scanning electron microscope or the like. When the primary particles are porous particles that are easily broken by impact, they have an average particle diameter of 50 μm or less.

In the present specification, the term "aerosol" refers to a solid-gas mixture in which the above-described fine particles are dispersed in a gas (carrier gas) such as helium, nitrogen, argon, oxygen, dry air, or a mixed gas containing these gases, and preferably refers to a state in which the fine particles are substantially dispersed individually, although the "aggregate" is included. The gas pressure and temperature of the aerosol may be arbitrarily set in consideration of the physical properties of the structure to be required, but when the gas pressure is 1 atmosphere and the temperature is 20 degrees celsius, the concentration of 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.

The flow of aerosol deposition is generally performed at normal temperature, and a structure can be formed at a temperature sufficiently lower than the melting point of the particulate material, i.e., 100 degrees celsius or lower. In the present specification, "normal temperature" means a temperature significantly lower than the sintering temperature of ceramics, 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 described above are naturally aggregated.

Examples

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

As the raw materials of the structures used in the examples, the raw materials shown in the following tables 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 approximating a circle.

By changing the combination of these raw materials and film forming conditions (the type, flow rate, and the like of the carrier gas), a plurality of samples having a structure on the substrate were produced. The samples thus obtained were evaluated for particle resistance after standard plasma tests 1 to 3. In this example, an aerosol deposition method is used for sample preparation.

TABLE 2

As shown in the table, nitrogen (N) was used as the carrier gas₂) 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 resulting aerosol is ejected by a pressure difference from a nozzle connected to an aerosol generator toward a substrate disposed inside a film forming chamber. At this time, the air in the film forming chamber is discharged to the outside by the vacuum pump.

Sample (I)

The structures of samples 1 to 6 thus obtained each contained a polycrystalline body of YAG as a main component, and the average crystallite size in the polycrystalline body was less than 30 nm.

XRD was used for measurement of crystallite size. That is, as the XRD device, "X' PertPRO/Pannake" was used. As the measurement conditions of XRD, CuK alpha is obtained as a characteristic X-rayThe tube voltage is 45kV, the tube current is 40mA, the step length is 0.0084 degrees, and the retention time is more than 80 seconds. As the average crystallite size, the crystallite size was calculated by the scherrer equation described above. 0.94 is used as the value of K in the Xiele equation.

The main component of the YAG crystal phase on the substrate was measured by XRD. As an XRD device, "X' PertPRO/Pannake" was used. As the measurement conditions of XRD, CuK alpha is obtained as a characteristic X-rayThe tube voltage is 45kV, the tube current is 40mA, the step length is 0.0084 degrees, and the retention time is more than 80 seconds. For the calculation of the main component, XRD analysis software "High Score Plus/Pasnake" was used. The relative Intensity Ratio required for the peak search of the diffraction peak was calculated using the Reference Intensity Ratio (RIR) described in the ICDD card. In the case of a layered structure, it is desirable to use the measurement result in a depth region of less than 1 μm from the outermost surface by thin-film XRD for the measurement of the main component of YAG polycrystal.

Standard plasma test

In addition, with respect to these samples 1 to 6, the standard plasma tests 1 to 3 under the above conditions were performed, and the particle resistance after the tests was evaluated in the following order. The ICP-RIE apparatus used in "Muc-21 Rv-Aps-Se/Sumitomo precision Industrial products". In the standard plasma tests 1-3, the cavity pressure was set to 0.5Pa and the plasma exposure time was set to 1 hour. The sample is placed on a silicon wafer that is attracted to an electrostatic chuck of 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

By passingThe indentation hardness of the structure on the substrate was evaluated by the minimum indentation hardness test (nanoindentation) in the following procedure. "ENT-2100/Elionix" was used as a minimum indentation hardness tester (nanoindenter). As the conditions of the minimum indentation hardness test, a triangular pyramid indenter was used as the indenter, and the test mode was an indentation depth setting test in which the indentation depth was 200 nm. Indentation hardness (indentation hardness) H_ITThe measurement was carried out. H is randomly set on the surface of the structure_ITThe number of measurement sites in (2) is at least 25 or more. More than 25 points of H are measured_ITThe average value of (A) is taken as the hardness. The results are shown in Table 2.

Determination of fluorine penetration depth

The surfaces of samples 2, 4, 5, and 6 after the standard plasma tests 1 to 3 were analyzed in the depth direction by X-ray photoelectron spectroscopy (XPS) using an ion beam, and the atomic concentration (%) of fluorine (F) atoms with respect to the sputtering time was measured. Next, in order to convert the sputtering time into depth, the step(s) between the portion sputtered by the ion beam and the portion not sputtered was measured by a stylus type surface shape measuring instrument. The depth (e) per unit sputtering time is calculated from e ═ s/t by the total sputtering time (t) used for the step(s) and XPS measurements, and the sputtering time is converted into the depth by the depth (e) per unit sputtering time. Finally, the depth from the sample surface and the fluorine (F) atom concentration (%) at the depth position were calculated.

The depth from the surface of the structure and the fluorine atom concentration after the standard plasma tests 1 to 3 are shown in the following table.

After standard plasma test 1:

TABLE 3

Sample (I)	30nm	20nm	15nm	10nm	5nm
						2	0％	0.35％	1.27％	17.1％	28.9％
4	0.26％	0％	1.06％	4.46％	32.4％
						5	1.33％	1.97％	3.06％	7.16％	29.5％
6	3.85％	4.97％	5.65％	9.26％	36.1％

After standard plasma test 2:

TABLE 4

Sample (I)	30nm	20nm	15nm	10nm	5nm
						2	0％	0％	0％	0％	0.61％
4	0％	0％	0.37％	0.39％	0.66％
						5	0.90％	0.98％	1.15％	1.21％	1.38％
6	2.58％	2.88％	3.11％	3.41％	3.55％

After standard plasma test 3:

TABLE 5

Sample (I)	30nm	20nm	15nm	10nm	5nm
						1	-	-	0.38％	0.60％	3.72％
2	0.55％	0.33％	0.51％	0.83％	4.95％
						4	0.45％	0.74％	0.86％	1.32％	5.73％
5	6.04％	6.65％	7.12％	7.15％	10.5％
						6	6.97％	8.09％	8.62％	9.03％	12.1％

The data are shown as graphs in fig. 2 to 4.

SEM image

SEM images of the surfaces of the structures after the standard plasma tests 1 to 3 were taken as described below. That is, the etching state of the plasma exposed surface was evaluated by using a Scanning Electron Microscope (SEM). SEM used "SU-8220/Hitachi manufacturing". The acceleration voltage was made 3 kV. The resulting photograph is shown in FIG. 5.

Evaluation of the results

As shown in table 2, in sample 6 having an indentation hardness of 8.4GPa and less than 8.5GPa, the influence of plasma erosion was large under any of the standard plasma tests 1 to 3, and it was found that the particle resistance was low because a plurality of large crater-like recesses and fine irregularities overlapping the recesses were observed on the surface of the structure after the plasma test.

On the other hand, in sample 5 having an indentation hardness of 10.6GPa and a hardness of more than 10GPa, a plurality of large crater-like recesses were formed after the standard plasma tests 1 and 2, but there were almost no fine uneven portions overlapping the recesses as compared with sample 6, and corrosion was relatively slow in the standard plasma test 3, and it was found that the structure had particle resistance.

In samples 2 and 4 having indentation hardnesses of 13.8GPa and 13.1GPa and higher than 13GPa of the structures, respectively, only a slightly crater-like large recess was observed under plasma exposure after the standard plasma tests 1 and 2. In addition, almost no corrosion was observed after the standard plasma test 3, and it was found that the coating had an extremely high particle resistance.

In using CHF₃Standard plasma test 1 of the gases followed by F1 concentration of fluorine atoms at a depth of 30nm from the surface for samples 2, 4, 5_30nmRespectively 0%, 0.26% and 1.33%, all less than 3%. Further, the fluorine atom concentration F1 at a depth of 20nm from the surface_20nmRespectively 0.35%, 0%, 1.97%, all less than 4%. It is known that samples 2, 4 and 5 have a small influence on plasma erosion in the structure. In addition, in samples 2 and 4, F1_30nmAnd F1_20nmAll of them were 1% or less, and it was found that the influence on plasma erosion in the structure was particularly small.

In contrast, in sample 6, the fluorine atom concentration F1_30nm3.85% of fluorine atom concentration F1_20nmThe higher of 4.97%, plasma etching of the inside of the structure was confirmed.

In the use of SF₆Gas and applied bias standard plasma test 2With respect to samples 2, 4, 5, the fluorine atom concentration F2 at a depth of 30nm from the surface_30nmRespectively 0%, 0.90%, all less than 2%. Further, the fluorine atom concentration F2 at a depth of 15nm from the surface_15nmRespectively 0%, 0.37% and 1.15%, all less than 3%. It is known that samples 2, 4 and 5 have a small influence on plasma erosion in the structure. In addition, in samples 2 and 4, F2_30nmAnd F2_15nmAll of them were 1% or less, and it was found that the influence on plasma erosion in the structure was particularly small.

In contrast, in sample 6, the fluorine atom concentration F2_30nm2.58% and a fluorine atom concentration F2_15nmThe higher of 3.11%, plasma etching of the inside of the structure was confirmed.

In the use of SF₆After standard plasma test 3 with gas and no applied bias, with respect to samples 2, 4, the fluorine atom concentration F3 at a depth of 20nm from the surface_20nmRespectively 0.55% and 0.45%, both less than 1%. Further, the fluorine atom concentration F3 at a depth of 10nm from the surface_10nm0.83% and 1.32% respectively, and not more than 2%. It is known that samples 2 and 4 have particularly little influence on plasma erosion inside the structure.

Fluorine atom concentration F3 on sample 5_20nm6.65% and less than 8%. Further, fluorine atom concentration F3_10nm7.15% and less than 9%. In sample 5, plasma erosion of the inside of the structure was confirmed, as compared with samples 2 and 4.

In contrast, in sample 6, the fluorine atom concentration F3_20nm8.09% and a fluorine atom concentration F3_10nmThe highest of 9.03%, it is known that plasma etching is large on the inside of the structure.

In consideration of the above results, in table 2, the case where the influence of the plasma corrosion is small in any of the standard plasma tests 1 to 3 was evaluated as "excellent", the case where the influence of the plasma corrosion is small in any of the standard plasma tests 1 to 3 was evaluated as "good", and the case where the influence of the plasma corrosion is present in any of the standard plasma tests 1 to 3 was evaluated as "x".

The embodiments of the present invention have been described above. However, the present invention is not limited to the above. The above-described embodiments are also included in the scope of the present invention as long as they have the features of the present invention, and techniques appropriately modified by those skilled in the art are included. 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, but can be appropriately changed. Further, each element included in each of the above embodiments may be combined as long as the technique is technically feasible, and the technique in which these are combined is also included in the scope of the present invention as long as the feature of the present invention is included.