Processing device, system, method, and program

Abstract

According to the present invention, provided are a processing device, a system, a method, and a program capable of calculating a configuration factor of a thin film formed on a substrate. A processing device (100) is mainly provided with a measurement data acquisition unit (110), a total scattering data calculation unit (120), and a configuration factor calculation unit (130). The processing device (100) is configured so as to be able to calculate a structural factor of a film formed on a substrate. A total scattering data calculation unit (120) acquires first total scattering data (Isp) and second total scattering data (Isub) from a measurement data acquisition unit (110), and calculates total scattering data (ITF) for only a membrane part on the basis of the first total scattering data (Isp) and the second total scattering data (Isub). The total scattering data ITF of only the film portion is obtained by subtracting the product of the second total scattering data Isub and the absorption factor Asub of the substrate from the first total scattering data Isp.

Description

Technical Field

[0001] This invention relates to a processing apparatus, system, method, and program capable of calculating structural factors. Background Technology

[0002] To properly understand the function of a material, information related to its three-dimensional structure is essential. Since most materials in the past were regular crystalline materials, their crystalline structure was determined using X-ray diffraction, a method that can analyze regular materials, thus obtaining information related to their three-dimensional structure. However, in recent years, in fields such as batteries and electronics, amorphous materials with reduced regularity have been increasingly used to maximize desired functions / properties.

[0003] In recent years, PDF (Pair Distribution Function) analysis has been studied as a method for analyzing amorphous materials using X-rays. In PDF analysis, the structure factor of the sample is calculated from data obtained through total scattering measurements. However, to prevent this calculation method from becoming cumbersome, the shape of the sample being measured is limited. For example, in the case of thin film samples formed on a substrate, a method could be considered to peel the film from the substrate and prepare it into a measurable powder. However, in such a method, there are concerns that the sample structure might change due to physical effects during the process from peeling to powder preparation. Therefore, a method is needed that allows analysis of the thin film sample in its original state on the substrate.

[0004] Previously, methods for measuring thin film samples have been proposed. By obliquely incident X-rays onto the thin film sample, the penetration length of the X-rays into the thin film sample is reduced, and the total scattering data of the X-rays is obtained from the thin film sample to obtain the scattering intensity of the thin film sample (Non-Patent Literature 1).

[0005] Existing technical documents

[0006] Non-patent literature

[0007] Non-patent literature 1: A.-C.Dippel, M.Roelsgaard, U.Boettger, T.Schneller, O.Gutowski, U.Ruett, IUCrJ.6(2019)290-298. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] However, the total scattering data obtained by irradiating a thin film sample on a substrate with X-rays includes total scattering data from both the substrate and the thin film sample. Therefore, in order to obtain total scattering data for the thin film sample formed on the substrate, it is necessary to use some method to exclude the influence of the substrate from the obtained total scattering data. However, the aforementioned non-patent document 1 does not disclose such a method.

[0010] The present invention was made in view of the following problems, and aims to provide a processing apparatus, system, method and program capable of calculating the structural factor of a thin film formed on a substrate.

[0011] Solution for solving the problem

[0012] (1) In order to achieve the above-mentioned objective, the processing apparatus of the present invention is a processing apparatus for calculating the structure factor of the film portion formed on the substrate, and the processing apparatus includes:

[0013] The measurement data acquisition unit acquires first total scattering data obtained by measuring a first sample containing the substrate and the film under measurement conditions of X-ray oblique incidence, and second total scattering data obtained by measuring a second sample containing the portion other than the film in the first sample under the same measurement conditions.

[0014] A total scattering data calculation unit calculates the total scattering data of the film based on the first total scattering data and the second total scattering data; and

[0015] The structure factor calculation unit calculates the structure factor of the membrane based on the total scattering data of the membrane.

[0016] (2) Preferably, the total scattering data calculation unit calculates the total scattering data of the film by subtracting the product of the second total scattering data and the absorption factor of the substrate from the first total scattering data.

[0017] (3) Preferably, the total scattering data calculation unit calculates the absorption factor of the substrate based on the incident angle of X-rays, the diffraction angle, the film thickness of the film, the absorption coefficient of the film and / or the refractive index of the film.

[0018] (4) Preferably, the measurement conditions have information related to the incident angle of the X-rays, which is less than twice the critical angle of total internal reflection.

[0019] (5) The system involved in this invention comprises:

[0020] An X-ray diffraction apparatus includes an X-ray generator for generating X-rays, an X-ray detector for detecting the X-rays, a sample stage for mounting a sample, and a goniometer for controlling the angle between the X-rays generated by the X-ray generator and the surface of the sample, and the angle between the X-rays received by the X-ray detector and the surface of the sample; and

[0021] The processing device,

[0022] The X-ray diffraction apparatus uses the X-ray generator, the X-ray detector, and the goniometer to generate the first total scattering data and the second total scattering data.

[0023] (6) Preferably, the system of the present invention further comprises a measurement condition determining unit for determining the measurement conditions, the measurement conditions having information related to the incident angle of X-rays, the measurement condition determining unit determining the incident angle of X-rays on the first sample and the second sample based on the film thickness of the film, the absorption coefficient of the film and / or the critical angle of total reflection of the first sample and X-rays.

[0024] (7) Alternatively, the system involved in the present invention may also include a sample information acquisition unit, which determines the film thickness and density of the film or the critical angle of total reflection of the film based on the data obtained using the X-ray diffraction device by means of X-ray reflectance measurement.

[0025] (8) Alternatively, the system involved in the present invention may also include a correlation calculation unit, which calculates the correlation relationship of the atoms contained in the membrane based on the structural factor of the membrane.

[0026] (9) The program involved in this invention is a program that can calculate the structure factor of the film formed on the substrate and is executed by a computer, the program comprising:

[0027] First total scattering data is obtained by measuring a first sample containing the substrate and the film under X-ray oblique incidence conditions;

[0028] Second total scattering data are obtained by measuring a second sample, which includes the portion of the first sample other than the membrane portion, under the measured conditions.

[0029] Based on the first total scattering data and the second total scattering data, the total scattering data of the film portion is calculated; and

[0030] The structure factor of the membrane is calculated based on the total scattering data of the membrane.

[0031] (10) The method of the present invention is a method for calculating the structure factor of a film portion formed on a substrate, the method comprising:

[0032] First total scattering data is obtained by measuring a first sample containing the substrate and the film under X-ray oblique incidence conditions;

[0033] Second total scattering data are obtained by measuring a second sample, which includes the portion of the first sample other than the membrane portion, under the measured conditions.

[0034] Based on the first total scattering data and the second total scattering data, the total scattering data of the film portion is calculated; and

[0035] The structure factor of the membrane is calculated based on the total scattering data of the membrane.

[0036] Invention Effects

[0037] According to the present invention, a processing apparatus, system, method, and program are provided that can calculate the structural factor of a thin film formed on a substrate. Attached Figure Description

[0038] Figure 1 This is a block diagram schematically illustrating a processing apparatus 100 according to one embodiment of the present invention.

[0039] Figure 2 It is a diagram that roughly shows the relationship between X-rays and the sample.

[0040] Figure 3 This shows the incident angle θ of the X-rays onto the sample. in The incident angle θ to the membrane R A diagram showing the relationships between them.

[0041] Figure 4 This is a block diagram that schematically illustrates a system 10 according to one embodiment of the present invention.

[0042] Figure 5 This is a flowchart illustrating the measurement process of one embodiment of the present invention.

[0043] Figure 6 This is a flowchart illustrating a sample position adjustment process according to an embodiment of the present invention.

[0044] Figure 7 This is a flowchart illustrating a total scattering data acquisition process according to an embodiment of the present invention.

[0045] Figure 8 This is a graph showing the results of X-ray reflectance measured using the MoKα wavelength and the X-ray reflectance measurement method.

[0046] Figure 9 This is a graph showing the relationship between the diffraction angle 2θ and the absorption factor A(θ) of the substrate.

[0047] Figure 10 This is a diagram showing the total scattering data of a sample with an ITO film formed on a glass substrate, the total scattering data of the glass substrate, and the data extracted from the total scattering data of the film portion only.

[0048] Figure 11 This is a graph showing the scattering intensity of the sample after normalization to the atomic scattering factor.

[0049] Figure 12 This is a diagram showing the structural factors of the membrane.

[0050] Explanation of reference numerals in the attached figures

[0051] 10. Computing System

[0052] 100 processing device

[0053] 110 Measurement Data Acquisition Department

[0054] 120 Total Scattering Data Calculation Unit

[0055] 130 Structural Factor Calculation Section

[0056] 200 control device

[0057] 210 Control Department

[0058] 220 Device Information Storage Unit

[0059] 230 Determination of Measurement Conditions

[0060] 240 Measurement Data Storage Unit

[0061] 250 Sample Information Acquisition Department

[0062] 260 Display Section

[0063] 300 X-ray diffraction apparatus

[0064] 310 X-ray Generator

[0065] 320 Incident-side Optical Unit

[0066] 330° goniometer

[0067] 340 Sample Stage

[0068] 350 Exit-side optical unit

[0069] 360 X-ray detector

[0070] 510 Input Device

[0071] 520 display device

[0072] 610 Input Device

[0073] 620 display device. Detailed Implementation

[0074] Next, embodiments of the present invention will be described with reference to the accompanying drawings. To facilitate understanding of the description, the same reference numerals will be used to label the same constituent elements in each drawing, and repeated descriptions will be omitted.

[0075] [Implementation Method]

[0076] Reference Figure 1 The processing apparatus 100, as one embodiment of the present invention, will be described. The processing apparatus 100 is, for example, a computer formed by connecting components such as a CPU (Central Processing Unit), ROM (Read Only Memory), RAM (Random Access Memory), interface, and memory to a bus L. It mainly includes a measurement data acquisition unit 110, a total scattering data calculation unit 120, and a structure factor calculation unit 130. The measurement data acquisition unit 110, the total scattering data calculation unit 120, and the structure factor calculation unit 130 are implemented by the aforementioned components of a computer. The processing apparatus 100 is configured to calculate the structure factor of a film formed on a substrate.

[0077] The measurement data acquisition unit 110, the total scattering data calculation unit 120, and the structure factor calculation unit 130 are configured to transmit and receive information via the control bus L.

[0078] The processing device 100 can be connected to a measuring device such as an X-ray diffraction device 300 via a control device 200 described later.

[0079] Input device 510 and display device 520 are connected to the CPU of processing device 100 via an interface. Input device 510 is, for example, a keyboard or mouse, for inputting data into processing device 100. Display device 520 is, for example, a monitor, for displaying total scattering data, measurement conditions, structure factor, PDF, etc.

[0080] The measurement data acquisition unit 110 acquires the total scattering data of the sample from outside the processing device 100. The total scattering data of the sample is measured by the X-ray diffraction device 300.

[0081] In this embodiment, the sample includes a first sample having a thin film (hereinafter referred to as a film portion) formed on the surface of a substrate, and a second sample consisting only of a substrate. That is, the first sample includes, for example, a substrate formed of glass and a film portion formed on the surface of the substrate.

[0082] Examples of samples include samples formed from a single substrate and samples formed from two substrates. In a sample formed from a single substrate, a film is formed on a portion of the substrate, and only the substrate itself appears in other portions of the substrate. A sample formed from two substrates includes a first substrate on a single substrate having a film formed thereon and a second substrate formed only by the substrate. When the sample is a single substrate, measurements are taken on the portion with the film formed (the first sample) and the portion consisting only of the substrate (the second sample), obtaining two types of total scattering data. When the sample is a two-substrate sample, measurements are taken on the first substrate (the first sample) with the film formed and the second substrate (the second sample) consisting only of the substrate, obtaining two types of total scattering data. In this specification, the total scattering data of the first sample is designated as the first total scattering data, and the total scattering data of the second sample is designated as the second total scattering data; they are collectively referred to as the total scattering data of the sample.

[0083] Total scattering data of a sample can be obtained by a measurement method in which X-rays are incident on the sample at an angle θ. In this method, the incident angle θ of the X-rays on the sample is... in The X-rays are incident at an angle below a predetermined angle onto the sample. Then, the receiving-side optical system is operated along an arc centered on the sample, and the scattered intensity of the X-rays emitted from the sample is measured. The set of multiple scattered intensities obtained is defined as total scattering data. The scattered intensity includes the position of the measurement point (the diffraction angle 2θ between the receiving-side optical system and the sample surface) and the intensity of the X-rays measured at that position; total scattering data is the set of scattered intensity values ​​at multiple measurement points. The predetermined angle is preferably slightly larger than the critical angle for total internal reflection of the film, depending on the characteristics of the film or the X-rays. A specific value for the predetermined angle is preferably 1° or less, more preferably 0.1° or more but less than 0.5°, and even more preferably 0.1° or more but less than 0.3°. The incident angle θ of the X-rays is... in Fixed at such an angle, thus relating the X-ray incident on the first sample at a refraction angle θ R Refracted and exited at an angle θ (≈2θ-θ) R The optical path until the X-rays exit can shorten the depth of the X-rays incident on the surface of the first sample, that is, the penetration length (penetration depth l) of the X-rays. p ) (refer to Figure 2Therefore, the influence of the substrate can be reduced in the first total scattering data obtained by measurement. More specifically, when the first sample is measured, the scattering intensity generated by the substrate can be reduced in the first total scattering data, while the scattering intensity generated by the film can be relatively increased, thus obtaining high-precision measurement data with low scattering intensity originating from the substrate.

[0084] Preferably, the second total scattering data and the first total scattering data are measured under the same measurement conditions. The same measurement conditions here refer to using the same system, i.e., the same processing device and the same X-ray diffraction device, and the same incident angle θ. in Measurements were performed. Due to deterioration of the processing and X-ray diffraction equipment, the wavelength and photosensitive sensitivity of the generated X-rays may slightly change. Therefore, even using the same type of equipment, the measurement results may differ slightly. Therefore, by using the same processing and X-ray diffraction equipment with the same incident angle θ... in By measuring the second total scattering data and the first total scattering data, the effects of device degradation can be eliminated, and the same X-ray penetration length can be used to perform the measurement while suppressing the influence of errors. In addition, when measuring multiple films formed on the same substrate, for each of the multiple first total scattering data obtained by measuring multiple films, one second total scattering data measured at one location can be used.

[0085] The total scattering data calculation unit 120 obtains the first total scattering data I from the measurement data acquisition unit 110. sp Second total scattering data I sub Based on these, the total scattering data I for the film portion alone was calculated. TF Total scattering data for the film only I TF For example, as shown in equation (1), from the first total scattering data I sp Subtract the second total scattering data I sub With the substrate absorption factor A sub The product of these factors is used to determine the absorption factor A of the substrate. sub This will be discussed later.

[0086] [Mathematical Expression 1]

[0087] I TF =I sp -A sub I sub ...Formula (1)

[0088] I TF Total scattering data of the membrane

[0089] I sp First total scattering data

[0090] I sub Second total scattering data

[0091] A sub : Absorption factor of substrate

[0092] Another example of the method for calculating the total scattering data of the membrane is shown in Equation (2).

[0093] [Mathematical Expression 2]

[0094]

[0095] Equation (2) differs from Equation (1) only in the intensity of the total scattering data at the film portion; otherwise, they are essentially the same. The reason for this is explained below. When both sides of Equation (2) are multiplied by A... sub When, the left side of equation (2) becomes I TF ·A sub Relative to the left side of equation (1), the total scattering data I of the membrane portion TF Become A sub The value of a multiple. Here, as regarding Figure 9 As will be discussed later, A sub It is roughly a constant. Therefore, equation (2) and equation (1) are in a constant multiple relationship, and can be said to be essentially the same.

[0096] Absorption factor A of the substrate sub This value represents the magnitude of the scattering intensity from the substrate, taking into account the attenuation at the film portion. Here, in the substrate where the film portion is provided, the scattering intensity from the substrate includes the following components.

[0097] 1. Components incident on and transmitted through the membrane

[0098] 2. The components mentioned in 1 above that reach the substrate and are absorbed by the substrate.

[0099] 3. The components of the scattered X-rays generated during process 2 above that are absorbed by the substrate.

[0100] 4. The components of the scattered X-rays that pass through the film generated during process 2 above.

[0101] The components 2 and 3 above can be obtained by measuring the scattering intensity of only the substrate portion (the second sample), thus determining the absorption factor A of the substrate used in equation (2). sub When considering the components in points 1 and 4 above, for example, the absorption factor A of the substrate... sub It is the ratio of the scattering intensity from the substrate with the film to the scattering intensity from the substrate alone. At this time, the absorption factor A of the substrate is... subThe value is 1 when there is no film and 0 when the film is infinitely thick. The absorption factor A of the substrate... sub The calculation method is shown in equation (3). Referring to equation (3), the absorption factor A of the substrate is... sub It is achieved by adjusting the absorption coefficient μ of the membrane. TF It is calculated by multiplying the optical path length of the X-rays that have passed through the film and reached the substrate, then passed through the film again and exited the sample. The absorption coefficient μ of the film is... TF It is calculated based on the transmittance of the membrane obtained using the Lambert-Beer Law. (Refer to...) Figure 2 The length of the X-ray path after it passes through the film and reaches the substrate, and then exits the sample, is the thickness t of the film. TF The incident angle θ towards the membrane R It is calculated from the diffraction angle 2θ.

[0102] [Mathematical Expression 3]

[0103]

[0104] μ TF Absorption coefficient of the membrane

[0105] t TF Thickness of the membrane

[0106] θ R The angle of incidence of X-rays onto the membrane

[0107] 2θ: Diffraction angle

[0108] Where, at the incident angle θ R In the case of a diffraction angle of 2θ, for example, when the X-rays are incident on the sample at a very shallow depth, the optical path from the X-ray scattering to its exit from the sample becomes extremely short. Therefore, the second term of equation (3) (1 / sin(2θ-θ)) is equivalent to the length of this optical path. R The value of )) becomes so small as to be negligible. Therefore, the expression with the second term removed can also be used. Here, as regarding Figure 9 As will be discussed later, the absorption factor A of the substrate sub We take a roughly constant value. Therefore, even if we use an expression that ignores the second term, it has almost no effect on the conclusion.

[0109] The incident angle θ towards the membrane R The incident angle θ from the X-rays onto the sample. in The complex refractive index n of a substance to X-rays * The complex refractive index n of the material to X-rays is calculated from this. * Equation (4) shows that the incident angle θ towards the membrane is... RIt is shown in equation (5).

[0110] [Mathematical Expression 4]

[0111] n * =1-δ-iβ···Equation (4)

[0112] in,

[0113]

[0114] n * Complex refractive index

[0115] r e The classical radius of an electron

[0116] λ: Wavelength of X-rays

[0117] N A Avogadro's constant

[0118] ρ: density

[0119] Z i M i c i The atom number, atomic weight, and atomic ratio of the i-th atom.

[0120] f i ′, f i ": Atom scattering factor of the i-th atom

[0121] [Mathematical Expression 5]

[0122]

[0123] θ in The angle of incidence of X-rays onto the sample

[0124] The refractive index of a substance to X-rays is given by the complex refractive index n as shown in equation (4). * The real part of is a value slightly smaller than 1. When X-rays are incident at a certain angle θ... R The complex refractive index n is given by the following incident angles on the sample. * Since it becomes an imaginary number, the angle of incidence θ towards the membrane, which is the real part, cannot be defined. R When X-rays are completely reflected from the sample surface, a phenomenon occurs. The angle of incidence of the X-rays onto the sample at this point is called the critical angle of total internal reflection, θ. c Critical angle for total internal reflection θ c As shown in equation (6). Furthermore, as shown in equation (6), the critical angle for total internal reflection θ c With complex refractive index n * The real part of is a commutative relation.

[0125] [Mathematical Expression 6]

[0126]

[0127] θ c Critical angle for total internal reflection

[0128] Figure 3 The critical angle θ for total internal reflection is shown. c The incident angle θ of X-rays onto the sample when it is 0.098° in The incident angle θ to the membrane R The relationship is that when X-rays are made to travel at an angle greater than the critical angle for total internal reflection θ... c When the sample is incident at a slightly larger angle, the incident angle θ towards the membrane is... R It becomes approximately 0. Utilizing this phenomenon, by making the X-rays travel at an angle θ greater than the critical angle for total internal reflection... c A slightly larger incident angle on the sample can extend the optical path length of X-rays in the film, thereby obtaining a greater scattering intensity in the film. Furthermore, it is known that with a critical angle of total internal reflection θ... c When the incident angle of X-rays is more than twice that of the sample, the incident angle θ of the X-rays onto the sample is... in The incident angle θ to the membrane R This becomes a value that is close to the target value. Therefore, the preferred incident angle θ of the X-rays onto the sample is... in It is the critical angle of total internal reflection θ c Less than twice as much.

[0129] The incident angle θ of the X-rays onto the sample in It can be set to a value such that X-rays are sufficiently absorbed by the membrane. This value is, for example, based on the X-ray penetration depth l into the membrane as shown in equation (7). p The depth of intrusion, l, is determined by equation (7). p This represents the film thickness at which the intensity of X-rays that penetrate the membrane and exit is attenuated by 1 / e. Incident angle θ in As an example, consider the thickness t of the membrane. TF and penetration depth l p It is determined by, for example, the incident angle θ of the X-rays onto the sample. in The thickness t of the membrane is determined to be such that TF Become the depth of intrusion l p The positive real multiple (e.g., 1, 2, 3 times) or higher. For sufficient absorption of X-rays by the film, this positive real multiple is preferably 1 or higher. By using a constant multiple such as a positive real multiple, the incident angle θ can be easily determined. in Here, the X-ray penetration depth into the membrane is l p The absorption coefficient μ of the membrane can be obtained TF (Equation (8)) and the critical angle of total internal reflection θ c Therefore, the incident angle θ of the X-rays onto the sample can be calculated.in Based on the thickness t of the membrane TF Absorption coefficient μ of the membrane TF and the critical angle of total internal reflection θ c To determine. Furthermore, as shown in equation (8), the complex refractive index n * The imaginary part and absorption coefficient μ TF It is an exchangeable relationship.

[0130] [Mathematical Expression 7]

[0131]

[0132] l P : Depth of intrusion

[0133] [Mathematical Expression 8]

[0134]

[0135] The structure factor calculation unit 130 calculates the structure factor of the film using the total scattering data of the film obtained by the above method. The method for converting the total scattering data into a scattering vector can use known methods. For example, the structure factor calculation unit 130 performs background, absorption correction, polarization correction, atomic scattering factor, and Compton scattering normalization on the total scattering data of the film to calculate the structure factor of the film. The calculated structure factor of the film can be displayed as a structure factor or displayed in PDF format after performing an inverse Fourier transform.

[0136] The structural factor is calculated by equation (9).

[0137] [Mathematical Expression 9]

[0138]

[0139] <f>=∑ i c i f i ...Formula (9)

[0140] α: Standardization coefficient, I TF Total scattering intensity of the membrane, c i f i : Molar concentration and atomic scattering factor of the i-th element in the sample, I inc Compton scattering intensity

[0141] As explained above, the processing apparatus 100 according to this embodiment can extract the total scattering intensity of the film portion formed on the substrate from the total scattering data and calculate the structure factor of the film portion with good accuracy.

[0142] [The overall system]

[0143] The processing device 100 of the present invention can be included in, for example, a computing system 10. Figure 4 This is a conceptual diagram illustrating an example of the configuration of computing system 10. (Using...) Figure 4 The computing system 10 is described below. The computing system 10 mainly includes a processing device 100, a control device 200, and an X-ray diffraction device 300.

[0144] [Control Device]

[0145] The control device 200 is, for example, a computer that connects a CPU, ROM, RAM, interface, display, and memory to a bus L. It includes a control unit 210, a device information storage unit 220, a measurement condition determination unit 230, a measurement data storage unit 240, a sample information acquisition unit 250, and a display unit 260. The control unit 210, device information storage unit 220, measurement condition determination unit 230, measurement data storage unit 240, sample information acquisition unit 250, and display unit 260 are implemented by the aforementioned components of a computer. The control device 200 is connected to the X-ray diffraction apparatus 300 to control the X-ray diffraction apparatus 300 and to process and store the acquired data. The control device 200 is connected to the input device 610 and the display device 620 via a suitable interface. These input devices 610 and the display device 620 are different from the input devices and display devices connected to the processing device 100.

[0146] The control unit 210 controls the operation of the X-ray diffraction apparatus 300, namely the apparatus information storage unit 220, the measurement condition determination unit 230, the measurement data storage unit 240, the sample information acquisition unit 250, and the display unit 260.

[0147] The device information storage unit 220 stores device information obtained from the X-ray diffraction device 300. This device information includes information related to the X-ray diffraction device 300, such as its model, type of X-ray source, wavelength of the X-rays, and background noise caused by the X-ray diffraction device 300, as well as information inherent to the X-ray diffraction device 300 itself. Furthermore, the device information can include all information determined by the measurement condition determination unit 230 (described later), such as the sample shape, refractive index, density, type and composition of constituent elements, film thickness, critical angle for total internal reflection, and absorption coefficient, or information required to obtain measurement data using the X-ray diffraction device 300.

[0148] The measurement condition determination unit 230 determines the measurement conditions applied to the X-ray diffraction apparatus 300 during measurement. These measurement conditions include conditions related to the irradiation-side optical system, such as the incident angle of the X-rays onto the sample and the width of the incident-side slit, and conditions related to the light-receiving-side optical system, such as the scanning axis, scanning range, step size, speed of the light-receiving-side optical system, and the conditions of the light-receiving-side slit. As described above, the measurement condition determination unit 230 can determine the measurement conditions based on the thickness t of the film. TF Absorption coefficient μ of the membrane TF Critical angle of total internal reflection θ c This determines the angle of incidence of the X-rays.

[0149] The measurement data storage unit 240 stores the measurement data obtained from the X-ray diffraction apparatus 300. The measurement data may include, for example, total scattering data or data obtained in measurements based on X-ray reflectance measurement methods. Furthermore, it may also include the same information as that in the apparatus information storage unit 220.

[0150] The sample information acquisition unit 250 uses an X-ray diffraction apparatus 300 to perform an X-ray reflectance measurement method to determine the thickness, density, and critical angle of total internal reflection of the film. The method for determining the thickness, density, and critical angle of total internal reflection using the X-ray reflectance measurement method can be a conventional method. Furthermore, the X-ray diffraction apparatus 300 used to perform the X-ray reflectance measurement method can be the same as or different from the apparatus used to obtain total scattering data. Table 1 shows the configuration of the apparatus used to determine the critical angle of total internal reflection in the X-ray reflectance measurement method used in this embodiment, and Table 2 shows the measurement conditions.

[0151] [Table 1]

[0152]

[0153] [Table 2]

[0154]

[0155] The display unit 260 enables the display device 520 to display the measurement data. This allows the user to confirm the measurement data. Furthermore, the user can instruct or specify the control device 200 based on the measurement data. Moreover, it can be connected to the processing device 100 to display structure factors and PDFs.

[0156] [X-ray diffraction apparatus]

[0157] The X-ray diffraction apparatus 300 mainly includes an X-ray generating unit 310 that generates X-rays from the X-ray focal point, i.e., the X-ray source, an incident-side optical unit 320, a goniometer 330, a sample stage 340 for setting up the sample, an exit-side optical unit 350, and an X-ray detector 360 for detecting X-rays.

[0158] When measuring total scattering data, the X-ray generating unit 310 preferably uses a high-energy X-ray source that uses silver or molybdenum as the target metal. On the other hand, when performing measurements based on X-ray reflectance, a low-energy X-ray source using copper is preferred. However, when measuring total scattering data and performing measurements based on X-ray reflectance using the same apparatus, molybdenum is preferred as the target metal. Furthermore, the incident-side optical unit 320, goniometer 330, sample stage 340, exit-side optical unit 350, and X-ray detector 360 can use existing apparatus, so descriptions are omitted.

[0159] [Determination Methods and Procedures]

[0160] A sample is placed in the X-ray diffraction apparatus 300, and the goniometer 330 is driven under predetermined conditions based on the control of the control device 200. X-rays are then incident on the sample, and the diffracted X-rays generated from the sample are detected. Diffraction data is thus obtained. The X-ray diffraction apparatus 300 sends apparatus information and the obtained diffraction data to the control device 200 as measurement data. Based on this measurement data, the structure factor of the film formed on the substrate can be calculated using the processing device 100, the calculation system 10, the method, and / or the program of the present invention. This will be described in detail below.

[0161] First, use Figure 5 The sample position adjustment process is explained. This process involves determining the density ρ of the film and the incident angle θ on the sample. in The processing is mainly performed by the control unit 210, the sample information acquisition unit 250, and the X-ray diffraction device 300.

[0162] When the process begins, in step S51, the X-ray diffraction device 300, controlled by the control unit 210, adjusts the position of the sample set on the sample stage 340.

[0163] In the next step S52, the sample information acquisition unit 250 uses the X-ray diffraction apparatus 300 to perform the X-ray reflectance measurement method to measure the X-ray reflectance in the sample.

[0164] In the next step S53, the sample information acquisition unit 250 uses the X-ray reflectivity obtained in step S52 to calculate the critical angle θ for total internal reflection. c .

[0165] In the next step S54, the sample information acquisition unit 250 reads the constituent elements and composition ratio of the film from the sample information acquisition unit 250, calculates the density ρ of the film based on them, and then further calculates the refraction angle θ of the film based on them. R .

[0166] In the next step S55, the sample information acquisition unit 250 uses the total internal reflection critical angle θ obtained in step S53. c The oblique incident angle θ is determined by the density ρ of the film obtained in step S54. in .

[0167] Then, in step S56, the control unit 210 and the X-ray diffraction device 300 use the tilted incident angle θ obtained in step S53. in To measure the total scattering data. Then, the processing ends.

[0168] The sample position adjustment process can be implemented as a computer program or stored as a computer program on a storage medium.

[0169] Next, use Figure 6 The measurement process is described below. The measurement process uses the film density ρ obtained through sample position adjustment and the incident angle θ on the sample. in The processing to obtain total scattering data of the sample including the film and the substrate, as well as total scattering data of the substrate only, is mainly performed by the control unit 210, the sample information acquisition unit 250, and the X-ray diffraction device 300.

[0170] When processing begins, first in step S61, the X-ray diffraction apparatus 300, based on control by the control unit 210, drives the goniometer 330 under predetermined conditions for the sample placed on the sample stage 340. Then, the X-ray diffraction apparatus 300 directs X-rays from the exit-side optical unit 350 onto the sample, and the X-ray detector 360 detects the diffracted X-rays generated from the sample. The resulting data is diffraction data. The X-ray diffraction apparatus 300 changes the position of the X-ray detector 360 relative to the sample, detecting diffracted X-rays at multiple locations. This yields the total scattering data I of the sample. sp Total scattering data of the sample I sp It is sent and stored in the measurement data storage unit 240.

[0171] In the next step S62, the X-ray diffraction apparatus 300, focusing solely on the substrate mounted on the sample stage 340, drives the goniometer 330 under predetermined conditions based on control by the control unit 210. Then, the X-ray diffraction apparatus 300 directs X-rays from the exit-side optical unit 350 onto the substrate, and the X-ray detector 360 detects the diffracted X-rays generated from the substrate. The resulting data is diffraction data. The X-ray diffraction apparatus 300 changes the position of the X-ray detector 360 relative to the substrate, detecting diffracted X-rays at multiple locations. This yields total scattering data for the substrate only. The total scattering data for the substrate only is transmitted and stored in the measurement data storage unit 240. Afterward, the process ends.

[0172] In addition, steps S61 and S62 may not be executed in the aforementioned order, or step S61 may be executed after step S62, or they may be executed simultaneously.

[0173] The measurement process can be implemented as a computer program or stored as a computer program on a storage medium.

[0174] Next, use Figure 7 The total scattering data acquisition and processing is explained. The total scattering data acquisition and processing is a process that obtains the total scattering data of the film only from the total scattering data of the sample including the film and the substrate obtained by measurement processing, and the total scattering data of the substrate only, and then calculates the structure factor of the film. It is mainly performed by the processing device 100.

[0175] When the process begins, in step S71, the measurement data acquisition unit 110 first acquires the total scattering data I of the sample, including the film and the substrate, from the measurement data storage unit 240. sp .

[0176] Next, in step S72, the measurement data acquisition unit 110 acquires the total scattering data I of the substrate only from the measurement data storage unit 240. sub .

[0177] In the next step S73, the total scattering data calculation unit 120 first reads the absorption coefficient μ of the film from the device information storage unit 220 and the sample information acquisition unit 250. TF The thickness t of the membrane TF The incident angle θ of X-rays onto the membrane R And the absorption factor A of the substrate is calculated from the diffraction angle 2θ. sub .

[0178] In the next step S74, the total scattering data calculation unit 120 obtains the first total scattering data I from the measurement data acquisition unit 110. sp Second total scattering data I sub Based on these data, the total scattering data I of the membrane portion alone was calculated. TF .

[0179] In the next step S75, the structure factor calculation unit 130 calculates the structure factor of the film using only the total scattering data of the film portion. The calculated structure factor is stored in the measurement data storage unit 240. Then, the processing ends.

[0180] In addition, the structural factors of the membrane are sent to the display device 520, where they are displayed as the status of the structural factors or as a PDF.

[0181] Here, the total scattering data acquisition and processing can be implemented as a computer program or stored as a computer program on a storage medium.

[0182] [Example]

[0183] The total scattering data of the ITO film formed on the glass substrate were measured using system 10. Table 3 shows the configuration of the apparatus used in this embodiment, and Table 4 shows the measurement conditions.

[0184] [Table 3]

[0185]

[0186] [Table 4]

[0187]

[0188] exist Figure 8 The image shows the use of MoKα wavelength. The results were obtained from X-ray reflectance measurements. The calculated ITO film thickness was 77.6 nm, and the density was 6.62 g / cm³. 3 Based on these results, the critical angle for total internal reflection is θ c It was calculated to be 0.1602°, δ=3.91×10 -6 β = 8.60 × 10 -8 .

[0189] Considering the above results, as the conditions for measuring total scattering data, the incident angle θ of the sample will be... in Set as the critical angle θ for total internal reflection c The value is 0.1602°, slightly larger than 0.17°. Then, this value is substituted into equations (5) and (7) as the incident angle θ towards the membrane. R The value was obtained as 0.0567°, which is the intrusion depth l. p The value was obtained as 65.64nm.

[0190] Here, in Figure 9 The diagram shows the relationship between the diffraction angle 2θ and the substrate's absorption factor A(θ), calculated based solely on total scattering data measured for the substrate. It can be seen that the substrate's absorption factor A(θ) is approximately 0.3 over roughly the entire diffraction angle range; therefore, the influence of the glass substrate is included in the measured values ​​by approximately 30%.

[0191] exist Figure 10 The total scattering data of a sample with an ITO film formed on a glass substrate (blue line) and a sample on a glass substrate (black line) are shown, along with the results of extracting the total scattering data of the film from these data (red line). Figure 11 The scattering intensity of the sample after normalization to the atomic scattering factor is shown. Figure 12 The structure factor of the membrane is shown. Generally, the quality of the correction used to convert to the structure factor is judged by whether the total scattering data in the high wavenumber region overlaps with the sum of the atomic scattering factor and Compton scattering. Because in the high wavenumber region ( The total scattering data of the ITO film in the above (contains data with atomic scattering factor < f) are related to the atomic scattering factor < f. 2 > With Compton scattering I inc The total value < f 2 >+I inc The overlap indicates that the correction is good (see reference). Figure 11 ).

[0192] Based on the above results, the processing apparatus, method, and program of the present invention can accurately calculate the structural factors of the film portion formed on the substrate while keeping the film portion attached to the substrate.

[0193] In the method of the present invention, since the X-rays do not need to pass through the substrate, a high-energy X-ray source is not required, and there are no restrictions on the type of substrate.

[0194] Furthermore, for example, when the existing method described in Non-Patent Document 1 is applied to a thin film sample with a small film thickness, data containing not only the scattering intensity from the thin film sample but also the scattering intensity from the substrate may be detected, which may prevent the scattering intensity of the thin film formed on the substrate from being obtained. When the scattering intensity of the thin film alone cannot be obtained, a suitable three-dimensional structure cannot be obtained. However, according to the present invention, even if the measurement data includes total scattering data from the substrate in addition to total scattering data from the film, the total scattering data from the substrate can be removed with good accuracy. Therefore, the present invention can be applied even to thin film samples that necessarily contain total scattering data from the substrate.

[0195] Furthermore, in order to obtain information related to the three-dimensional structure of the thin film sample disposed on the substrate, it is necessary to obtain the scattering intensity of the thin film formed on the substrate alone. In order to eliminate the influence of the scattering intensity originating from the substrate, it is necessary to precisely determine the incident angle θ of the X-rays on the thin film sample. in However, according to the present invention, the incident angle θ of the X-rays onto the sample... in The preferred option is the critical angle θ for total internal reflection. c Less than twice the normal value. Therefore, the incident angle θ of the X-rays can be easily and precisely determined. in .

[0196] Furthermore, in the method described in Non-Patent Document 1, as mentioned above, the incident angle θ needs to be precisely controlled in order to prevent the detection of scattering intensity originating from the substrate. in Regarding this, when using radiation with low parallelism, the incident angle θ needs to be precisely controlled. in It is difficult to achieve this, thus requiring the output of a radiation beam facility with a high degree of parallelism. However, according to the present invention, since the scattering intensity originating from the substrate can be removed with good accuracy, the output of a radiation beam facility with a high degree of parallelism is not required.

[0197] In addition, the processing device 100 may be, for example, a PC terminal, a server in the cloud, or the entire processing device 100 may be located in the cloud, or a part of the processing device 100 or a part of the functions of the processing device 100 may be located in the cloud.

[0198] Furthermore, it is stated that the total scattering data of the sample was measured by the X-ray diffraction apparatus 300, but it may also be obtained by other apparatus capable of obtaining the total scattering data of the sample, rather than by the X-ray diffraction apparatus 300.

[0199] Furthermore, in equations (1) and (2), scattering intensity can be used instead of total scattering data. Even when using scattering intensity, the aforementioned effects can still be achieved.

[0200] Alternatively, the processing unit 100 and the control unit 200 may be housed in a single computer. In this case, the processing unit 100 and the control unit 200 share the input device and the display device.

[0201] Furthermore, the size, shape, and quantity of the components shown in this specification and accompanying drawings are illustrative and not limited to these aspects. Additionally, the raw materials used for each component are illustrative and not limited to these aspects.

[0202] Although embodiments of the invention have been described with reference to the accompanying drawings, it will be apparent to those skilled in the art that modifications can be made to the structure and relationships of the parts without departing from the scope and spirit of the invention as described.< / f>

Claims

1. A processing apparatus capable of calculating the structure factor of a film formed on a substrate, characterized in that, have: The measurement data acquisition unit acquires first total scattering data obtained by measuring a first sample containing the substrate and the film under measurement conditions of X-ray oblique incidence, and second total scattering data obtained by measuring a second sample containing the portion other than the film in the first sample under the same measurement conditions. The total scattering data calculation unit calculates the total scattering data of the film based on the first total scattering data and the second total scattering data; as well as The structure factor calculation unit calculates the structure factor of the membrane based on the total scattering data of the membrane.

2. The processing apparatus according to claim 1, wherein, The total scattering data calculation unit calculates the total scattering data of the film by subtracting the product of the second total scattering data and the absorption factor of the substrate from the first total scattering data.

3. The processing apparatus according to claim 2, wherein, The total scattering data calculation unit calculates the absorption factor of the substrate based on the incident angle and diffraction angle of the X-rays, the film thickness, the absorption coefficient of the film, and / or the refractive index of the film.

4. The processing apparatus according to any one of claims 1 to 3, wherein, The measurement conditions include information related to the incident angle of the X-rays, which is less than twice the critical angle for total internal reflection.

5. A system, characterized in that, have: An X-ray diffraction apparatus includes an X-ray generator for generating X-rays, an X-ray detector for detecting the X-rays, a sample stage for placing a sample, and a goniometer for controlling the angle between the X-rays generated by the X-ray generator and the surface of the sample and the angle between the X-rays received by the X-ray detector and the surface of the sample. as well as The processing apparatus according to any one of claims 1 to 4, The X-ray diffraction apparatus uses the X-ray generator, the X-ray detector, and the goniometer to generate the first total scattering data and the second total scattering data.

6. The system according to claim 5, wherein, It also includes a measurement condition determining unit that determines the measurement conditions, the measurement conditions having information related to the incident angle of X-rays, the measurement condition determining unit determining the incident angle of X-rays on the first sample and the second sample based on the film thickness of the film, the absorption coefficient of the film and / or the critical angle of total internal reflection of the first sample and X-rays.

7. The system according to claim 6, wherein, It also includes a sample information acquisition unit, which determines the film thickness and density of the film or the critical angle of total internal reflection of the film based on data obtained using the X-ray diffraction device by means of X-ray reflectance measurement.

8. The system according to any one of claims 5 to 7, wherein, It also has a correlation calculation unit, which calculates the correlation relationships of the atoms contained in the membrane based on the structure factor of the membrane.

9. A computer-executed program capable of calculating the structure factor of a film formed on a substrate, characterized in that, have: First total scattering data is obtained by measuring a first sample containing the substrate and the film under X-ray oblique incidence conditions; Second total scattering data are obtained by measuring a second sample, which includes the portion of the first sample other than the membrane portion, under the measured conditions. The total scattering data of the membrane is calculated based on the first total scattering data and the second total scattering data; as well as The structure factor of the membrane is calculated based on the total scattering data of the membrane.

10. A method for calculating the structure factor of a film formed on a substrate, characterized in that, have: First total scattering data is obtained by measuring a first sample containing the substrate and the film under X-ray oblique incidence conditions; Second total scattering data are obtained by measuring a second sample, which includes the portion of the first sample other than the membrane portion, under the measured conditions. The total scattering data of the membrane is calculated based on the first total scattering data and the second total scattering data; as well as The structure factor of the membrane is calculated based on the total scattering data of the membrane.

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