JP2015122408A - Evaluation method, evaluation device, and method of manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To more easily measure defective level of a semiconductor or an insulating body than before, without processing a sample to an element structure.SOLUTION: In an evaluation method, firstly, a semiconductor or an insulating body on a surface of a sample 12 is irradiated with X ray 16 so that temporal change in energy distribution of a photoelectron 20 that is released from the semiconductor or the insulating body is detected. Then, in addition to the X ray 16, the surface of the sample 12 is irradiated with a single color light 24 of the energy smaller than a band gap of the semiconductor or the insulating body, and a temporal change in the energy distribution of the photoelectron that is caused by that is detected. Based on the detection result, an internal defect of the semiconductor or the insulating body is evaluated.

Description

  The present invention relates to an evaluation method and an evaluation apparatus, and is suitably used for evaluation of a semiconductor device having an insulating film, for example. Furthermore, the present invention relates to a method for manufacturing a semiconductor device.

  Semiconductor materials are structurally sensitive materials, and very few impurities and defects determine their physical properties. For this reason, it is important to evaluate the defect concentration, the time constant of trapping in the defect, the energy level of the defect, and the like, and various evaluation methods have been developed so far.

  For example, in a MOS (Metal Oxide Semiconductor) type semiconductor element using a Si (silicon) substrate, a method of measuring a relationship between a capacitance of a MOS structure and an applied voltage called a CV (electric capacity-voltage) method is widely used. (For example, refer to JP 2001-85484 A (Patent Document 1)). By the CV method, the interface trap of the MOS structure and the defect in the oxide film can be evaluated.

  However, although the CV method is simpler than making an actual element, it is necessary to form an evaluation element having electrodes. Furthermore, when the thickness of the oxide film becomes very thin, a tunnel current flows, so that it cannot be applied.

  DLTS (Deep Level Transient Spectroscopy) is a technique for measuring a transient process of capacitance by thermal excitation, and is used for trap analysis in various semiconductors such as Si, GaAs (gallium arsenide), InP (indium phosphide). However, this method also needs to form a simple element structure and electrodes.

  Therefore, time-resolved X-ray photoelectron spectroscopy has been proposed as one of the methods that can easily evaluate traps in various materials without forming electrodes and element structures. For example, in the method described in JP-A-9-162253 (Patent Document 2), charges (electrons and holes) are generated in an insulating film in a semiconductor substrate by X-ray irradiation, and the generated charges are converted into current or Measured as change in surface potential of sample. The generated electric charge is trapped in the presence of a defect in the insulating film, so that the current of the sample and the surface potential change. By detecting this change, information about the density of defects and the time constant of carrier capture can be obtained.

JP 2001-85484 A JP-A-9-162253

  However, conventional time-resolved X-ray electron spectroscopy has a problem that information about the energy level of defects cannot be obtained.

  On the other hand, Japanese Patent Laid-Open No. 2001-85484 (Patent Document 1) discloses a method of performing CV measurement while exciting carriers trapped in a defect by light irradiation in order to evaluate a deep trap level. doing. However, in order to evaluate all the trap levels, it is necessary to repeatedly perform CV measurement while changing the wavelength of irradiation light, and there is a problem that it takes time for the evaluation.

  The present invention has been made in consideration of the above-mentioned problems, and its main purpose is to measure the defect level of a semiconductor or an insulator more easily than before without processing the sample into an element structure. It is to provide an evaluation method and an evaluation apparatus that can be used.

  An evaluation method according to an embodiment includes first and second detection steps and an evaluation step. In the first detection step, the temporal change in the energy distribution of photoelectrons emitted from the semiconductor or insulator is detected by irradiating the semiconductor or insulator on the sample surface with X-rays. In the second detection step, a temporal change in the energy distribution of photoelectrons generated by irradiating the sample surface with monochromatic light having an energy smaller than the band gap of the semiconductor or insulator in addition to X-rays is detected. In the evaluation step, defects inside the semiconductor or the insulator are evaluated based on the detection results of the first and second detection steps.

  According to the above embodiment, the defect level of the semiconductor or the insulator can be measured more easily than before without processing the sample into an element structure.

It is a figure which shows typically the structure of the evaluation apparatus by Embodiment 1. FIG. It is a figure which shows an example of the measurement result by a X ray photoelectron spectroscopy. Is a diagram showing an X-ray irradiation time dependency of Delta] E _Si. It is a figure for demonstrating derivation | leading-out of Formula (2)-(8) (perspective view). It is a figure for demonstrating derivation | leading-out of Formula (2)-(8) (side view). 3 is a flowchart illustrating a procedure of an evaluation method according to Embodiment 1. The band structure of the SiO ₂ film of the example is a diagram schematically illustrating. The X-ray irradiation time dependency of Delta] E _Si to be observed in the SiO ₂ film 7 is a view schematically showing. Is a graph showing changes in Delta] E _Si in photoirradiation. FIG. 10 is a diagram for explaining a method for manufacturing a semiconductor device as an application example of the evaluation method according to the first embodiment;

  Hereinafter, each embodiment will be described in detail with reference to the drawings. In the following drawings, the scale of each member may be different from the actual scale for easy illustration. Furthermore, the same or corresponding parts are denoted by the same reference numerals, and the description thereof may not be repeated.

<Embodiment 1>
[Configuration of evaluation device]
FIG. 1 is a diagram schematically showing the configuration of the evaluation apparatus according to the first embodiment. With reference to FIG. 1, the evaluation apparatus 1 includes a vacuum chamber 10, a sample stage 14, an X-ray source 18, an electron spectrometer 22, a control unit 28, and a variable wavelength light source 26.

  The inside of the vacuum chamber 10 is kept at an ultrahigh vacuum by being depressurized by a vacuum pump 32 through a valve 30. As a result, the photoelectrons emitted from the sample 12 can fly to the electron spectrometer 22. A sample stage 14 provided in the vacuum chamber 10 holds the sample 12 at the measurement position.

  The X-ray source 18 generates monochromatic X-rays 16 and irradiates the sample 12 with the generated X-rays 16. As a result, carriers (electrons and holes) are generated in the sample 12, and photoelectrons 20 are emitted from the sample 12 at the same time. The electron spectrometer 22 takes in photoelectrons emitted from the sample 12 and diverges them energetically.

  The wavelength tunable light source 26 uses irradiation light 24 (that is, light having a single wavelength) having specific energy smaller than the band gap of the measurement target insulating film formed on the sample surface based on a command from the control unit 28. The sample 12 is irradiated at a predetermined timing. As a result, a part of the carriers trapped by the defects in the insulating film is re-excited, and as a result, charging of the sample 12 is relaxed. As the wavelength variable light source 26, a laser light source based on induced fluorescence, a coherent light source based on a nonlinear optical effect, or the like can be used.

  The control unit 28 is configured based on a computer having a processor, a memory, an input / output interface, a display device, and the like. The control unit 28 acquires data indicating the relationship between the photoelectron energy and the number detected by the electron spectrometer 22 (that is, photoelectron energy distribution data), processes the acquired data, and displays the data on the display device. . The control unit 28 further controls the operations of the X-ray source 18 and the wavelength variable light source 26.

[About time-resolved X-ray photoelectron spectroscopy]
X-ray photoelectron spectroscopy, which evaluates the photoelectron spectrum generated by irradiating a sample with X-rays (ie, photoelectron energy distribution), is widely used as a method for analyzing the composition and chemical bonding state of the surface of various materials. ing. In the case where the material is a semiconductor or an insulator, it is also well known that a charging phenomenon occurs in a sample due to emission of photoelectrons. This charging phenomenon changes the energy value giving the peak of the photoelectron spectrum.

  The charging phenomenon is the result of trapping carriers in the defects, and the charging process reflects the density of defects in the film and the time constant of carrier trapping. Therefore, the defect in the sample can be evaluated by detecting the time dependence of the photoelectron spectrum change during continuous X-ray irradiation. This technique is time-resolved X-ray photoelectron spectroscopy. In addition, since a metal does not have a band gap and does not produce a charging phenomenon, it is out of the scope of this method. The time-resolved X-ray photoelectron spectroscopy has the advantage that it is not necessary to form an element structure for evaluation and electrode formation is not necessary as compared with the method using the CV method described above.

Hereinafter, the measurement principle of time-resolved X-ray photoelectron spectroscopy will be described by taking as an example the case where time-resolved X-ray photoelectron spectroscopy is applied to a SiO ₂ film formed on a Si substrate by thermal oxidation. .

FIG. 2 is a diagram showing an example of a measurement result by X-ray photoelectron spectroscopy. The horizontal axis in FIG. 2 represents the binding energy of electrons in the sample calculated from the kinetic energy of photoelectrons, and the vertical axis represents the intensity of photoelectrons corresponding to each binding energy in arbitrary units (au). In Figure 2, a peak corresponding to the SiO ₂ in the vicinity and the peak corresponding to the 2p electrons of Si is shown.

The SiO ₂ film has a band gap of 9 eV, and a defect level for capturing carriers exists in the band gap. For this reason, when X-rays are continuously irradiated onto the SiO ₂ film, some of the excited carriers are captured at the defect level and accumulated in the sample. The sample is charged by the charge, and the potential of the sample changes.

As the potential of the sample changes, the energy of the SiO ₂ peak changes as shown by the curve 40 in FIG. The energy difference between the Si peak and the SiO ₂ peak is hereinafter referred to as ΔE _Si .

FIG. 3 is a diagram showing the dependency of ΔE _{Si on} the X-ray irradiation time. As shown by a curve 44 in FIG. 3 (hereinafter also referred to as a characteristic curve), the value of ΔE _Si , that is, the shift amount of the SiO ₂ peak with the lapse of X irradiation time (unit: time (hr: hour)). Gradually saturates. The characteristic curve 44 can be separated by one or a plurality of exponential functions as will be described below. The number of exponential functions to be separated corresponds to the type of defect level, and the amount of change in each exponential function after separation reflects the density of each defect level, and the time constant of each exponential function corresponds to each defect level. Reflects the time constant of carrier capture.

Next, the relationship between the amount of change in ΔE _Si and the density of defect levels will be described in detail. For simplicity, consider the case of a SiO ₂ film having only one type of defect level. As described above, since Delta] E _Si varies exponentially, after the start of X-ray irradiation, a Delta] E _Si (t) at the time of t has elapsed when writing in formula,

It becomes. Here, ΔE _Si (0) is ΔE _Si before the start of X-ray irradiation, K is the potential of the SiO ₂ film when all defect levels capture carriers, t is the X-ray irradiation time, and τ is the time of trapping. It is a constant.

  K in the above formula (1) is expressed using the defect level density D of the sample. K is an integral value of the electric field E formed by the trapped carriers, and the electric field E can be expressed as a function of the position r including D by using Gauss's law. The derivation is shown below.

  4 and 5 are diagrams for explaining the derivation of the equations (2) to (8). In general, since the thickness of the insulating film 50 to be evaluated is sufficiently thinner than the side length of the film, the electric field formed by the trapped carriers can be regarded as being equal to the electric field created by the infinite flat plate. Therefore, when a cylindrical minute volume V (reference numeral 52) as shown in FIG. 3 is considered and Gauss's law is applied, the following equation is obtained.

In the above equation (2), E (r) is the electric field at the position r, n is the unit vector, S is the area of the top and bottom surfaces of the cylindrical microvolume V, ε ₀ is the vacuum dielectric constant, and ε _r is SiO ₂ . The relative dielectric constant, Q, is the amount of charge contained in V. The total charge amount is given as the sum of each charge Q _i .

  The left side of Equation (2) is calculated as follows.

Also, the right side of equation (2) is

Is calculated. Here, e is the elementary charge, and p is the polarity of the defect level (+1 for hole trap, -1 for electron trap).

  Therefore, from equation (2):

Is obtained. When obtaining the K by the E (r) is integrated in a range of r = 0 to t _f,

It becomes. Here, t _f is the SiO ₂ film thickness.
Therefore, equation (1) is

Thus, by using this equation, D can be calculated from the dependence of ΔE _{Si on} the X-ray irradiation time. Formula (7) is as follows when i types of defect levels exist.

[Summary of evaluation method]
Next, an overview of the evaluation method according to the first embodiment will be described. The following evaluation method is executed under the control of the control unit 28 in FIG.

FIG. 6 is a flowchart showing the procedure of the evaluation method according to the first embodiment. With reference to FIGS. 1 and 6, first, the control unit 28 starts continuous irradiation of the X-ray 16 on the sample 12 by the X-ray source 18 (S <b> 100). The control unit 28 acquires a photoelectron spectrum (photoelectron energy distribution) at regular intervals by the electron spectrometer 22 and obtains ΔE _Si at that time (S105). The obtained ΔE _Si is plotted against the X-ray irradiation time on the display device.

The control unit 28 separates the curve representing the relationship between ΔE _Si and the X-ray irradiation time (also referred to as a characteristic curve) into one or more exponential functions by fitting the equation (8) (S110). . Further, the control unit 28 quantifies the density of each defect level and the capture time constant from the amount of change and the time constant of the exponential function after separation (S115). However, at this time, the energy level of each defect is unknown.

Control unit 28 continues the X-ray photoelectron spectroscopy while follow the change in Delta] E _Si, determines whether the rate of change of Delta] E _Si per minute becomes 0.05% or less. After 1 hour has elapsed since the rate of change of ΔE _Si per minute is 0.05% or less (YES in S120), the control unit 28 uses the variable wavelength light source 26 to supply specific energy different from X-rays. The light which has is irradiated (S125). Note that X-ray irradiation continues even after the above-described irradiation with monochromatic light.

The control unit 28 obtains ΔE _Si at that time every predetermined time again by the electron spectrometer 22 (S130). The control unit 28 specifies an exponential function obtained by fitting in step S110 that has its influence disappeared by light irradiation (S135). Then, the control unit 28 determines that the energy level of the defect corresponding to the lost exponential function is within the energy of the irradiation light with reference to the band edge of the valence band or the conduction band (S135).

  Thereafter, the control unit 28 repeats the steps S125 to S140 while changing the energy of the irradiation light stepwise (YES in step S140), and the density, capture time constant, and energy of all defect levels in the band gap. Find the level range.

[Specific examples of evaluation methods]
Next, the case where the evaluation method according to the first embodiment is applied to an SiO ₂ film having a thickness of 5 nm formed on a Si substrate by a thermal oxidation method will be specifically described as an example.

FIG. 7 is a diagram schematically showing the band structure of a specific example SiO ₂ film. Referring to FIG. 7, the SiO ₂ film has a band gap 58 of 9 eV, and has a total of three types of defect levels in the band gap. Specifically, it is assumed that there are one type of defects 1 and 2 each acting as a hole trap in the range of 3 to 2 eV and the range of 2 to 1 eV from the top of the valence band 54 to the high energy side. Defect 1 is due to oxygen deficiency, and defect 2 is due to non-bridging oxygen. Furthermore, it is assumed that there is one type of defect 3 that acts as an electron trap in the range of 0 to 1 eV from the bottom of the conduction band 56 to the low energy side.

When such an SiO ₂ film is continuously irradiated with X-rays, carriers are generated in the film. The generated carriers diffuse in the film and are eventually captured by the defect 1, the defect 2, and the defect 3. As a result, the sample is charged, and the energy value of the obtained photoelectron peak is changed.

FIG. 8 is a diagram schematically showing the dependence of ΔE _{Si on} the X-ray irradiation time observed in the SiO ₂ film of FIG. A characteristic curve 60 representing the dependency of ΔE _{Si on} the X-ray irradiation time is shown by a solid line in FIG.

As shown in FIG. 8, when there are several kinds of defect levels in the sample, the dependence of ΔE _{Si on} the X-ray irradiation time (characteristic curve 60) is the sum of changes caused by carriers trapped in each defect level. Become. Such a curve is separated into one or more exponential functions using the above-described equation (8), and the amount of change and time constant of each are obtained, whereby the density D of each defect level and the time constant of trapping are obtained. τ can be obtained.

  The result of separation of the characteristic curve 60 of FIG. 8 is shown as exponential function curves 62, 63, 66 in FIG. The density D1, D2, D3 of each defect and the capture time constants τ1, τ2, τ3 are obtained as follows by the separation. The curves 62, 64, and 66 correspond to the defects 1, 2, and 3, respectively, but the energy level is unknown at this stage, and the correspondence with the defects 1, 2, and 3 is also unknown.

Curve 62: D1 = 1.25 × 10 ²⁰ [/ cm ³ ], τ1 = 0.5 [time]
Curve 64: D2 = 5.22 × 10 ¹⁹ [/ cm ³ ], τ2 = 1 [time]
Curve 66: D3 = 2.09 × 10 ²⁰ [/ cm ³ ], τ3 = 2 [time]
Next, a method for obtaining the energy level range of each defect in addition to the above-described defect level density D and trapping time constant τ will be described. As described above, ΔE _Si decays exponentially as the X-ray irradiation time becomes longer. However, even after the change has disappeared, carrier trapping, thermal excitation, and X-ray excitation are actually caused by defect levels. Escape has occurred and both are in equilibrium. Therefore, when the state in which the change rate per minute of ΔE _Si is 0.05% or less continues for 1 hour (in the example of FIG. 8, when 5 hours have elapsed), the charging phenomenon is balanced. From this state, light different from X-rays (here, light having energy of 1 eV) is continuously irradiated from the wavelength variable light source 26 onto the sample 12 simultaneously with the X-rays. As a result, trapped carriers that can be excited at 1 eV and exist in an energy range within 1 eV from the band edge of the valence band or the conduction band escape from the defect level. As a result, the charging of the sample is relaxed, and the behavior of ΔE _Si changes.

FIG. 9 is a diagram showing a change in ΔE _Si upon light irradiation. Referring to FIG. 9, a change is seen in curve 66 by irradiating with light having an energy of 1 eV after 5 hours from the start of X-ray irradiation (time t1 in FIG. 9). That is, it can be seen that carriers (in this case, electrons) are emitted from the defect corresponding to the curve 66. Accordingly, it can be seen that the defect corresponding to the curve 66 is the defect 3 having an energy level in a range within 1 eV from the band edge.

Thereafter, when the rate of change per minute of ΔE _Si under irradiation of light having energy of X-rays and 1 eV continues for 1 hour (time t2 in FIG. 9), Irradiation of light having an energy of 1 eV is stopped, and irradiation of light having an energy of 2 eV is newly started. As a result, a change is seen in the curve 64. That is, carriers (in this case, holes) are emitted from the defect corresponding to the curve 64. Therefore, it can be seen that the defect corresponding to the curve 66 is the defect 2 having an energy level in the range of 1 to 2 eV from the band edge.

Similarly, each time the charging phenomenon reaches an equilibrium state, the sample is irradiated with light having energy of 3 eV and 4 eV in order, and 2 to 3 eV, 3 to 4 eV, and 4 to 4.5 eV (band gap) from the band edge. Quantification is performed for defect levels existing in each range (up to 1/2 of the above). As a result, the density of various defect levels in the SiO ₂ film, the capture time constant, and the energy level can be clarified.

  In the above description, the timing of the charging phenomenon reaching an equilibrium state is waited each time after the start of light irradiation, but this is not always necessary. If the change in the curve after separation can be determined, the energy of the irradiated light may be changed to the following value.

[Effect of Embodiment 1]
As described above, in the evaluation method according to the first embodiment, when the sample is first irradiated with only X-rays, the energy distribution of the photoelectrons emitted from the semiconductor or insulator film on the sample surface, particularly the energy value that gives a peak. Shift amount (that is, ΔE _Si ) is detected. This peak shift occurs when carriers generated by X-ray irradiation are trapped by defects in the film. A curve representing the correspondence relationship between the shift amount of the peak energy value and the X-ray irradiation time is separated into one or a plurality of exponential function curves. As a result, the type of defects in the film, the density of defects, and the time constant for trapping carriers in the defects can be determined.

  Next, monochromatic light having an energy smaller than the band gap of the semiconductor or insulator to be evaluated is irradiated together with the X-ray. The energy of monochromatic light is increased in steps. By this monochromatic light irradiation, carriers trapped in some defects corresponding to the monochromatic light energy are emitted. As a result, a part of the exponential function curve changes according to the energy of monochromatic light. By discriminating the changed exponential curve, the energy level of each defect can be specified.

  As described above, the defect level of the semiconductor or the insulator can be easily evaluated by one measurement without processing the sample into an element structure as compared with the method using the conventional CV method.

<Embodiment 2>
In the second embodiment, a method for manufacturing a semiconductor device will be described as an application example of the evaluation method according to the first embodiment. The semiconductor device can be applied to all semiconductor devices having an insulating film in the structure, such as MOSFET (MOS Field Effect Transistor) or TFT (Thin Film Transistor). As an insulating film, a SiO ₂ film formed by a thermal oxidation method, a steam oxidation method, a CVD (Chemical Vapor Deposition) method, or the like is a suitable application example.

Although several types of defects are included in the SiO ₂ film, the evaluation method according to the first embodiment targets non-bridging oxygen and oxygen vacancies that can cause leak defects. In the SiO ₂ film, whether the presence of defects in the SiO ₂ film is equal to or less than the prescribed value is determined. The inspection of the amount of each defect is performed on the inspection wafer created in the film forming process. A specific specified value is that the defect density in the energy region of 1 to 2 eV and 2 to ³ eV is 2 × 10 ²⁰ [/ cm ³ ] or less.

  FIG. 10 is a diagram illustrating a method for manufacturing a semiconductor device as an application example of the evaluation method according to the first embodiment. FIG. 10 shows an example of a manufacturing process of a MOS semiconductor device as an example.

  Referring to FIG. 10, first, a well region is formed on a cleaned Si substrate (S200) (S205), and further an element isolation region such as STI (Shallow Trench Isolation) is formed (S210).

  Subsequently, a channel region is formed (S215), and then a gate oxide film is formed (S220). The evaluation method according to the first embodiment is used for evaluating the defect of the gate oxide film (S225). As described above, the defect is evaluated immediately after the formation of the oxide film. Normally, an oxide film is formed on a dummy wafer for inspection by the same process when forming the gate oxide film, and defects are evaluated for the oxide film formed on the wafer for inspection.

  Subsequently, a gate electrode, a source region, and a drain region are formed (S230, S235), and then an insulating layer is formed for interlayer insulation with the upper metal wiring layer (S240). Even when the insulating layer is formed, the insulating layer is formed on the inspection wafer by the same process, and the defect is evaluated using the inspection wafer.

  Subsequently, a contact hole is formed in the formed insulating layer (S250), and a metal wiring layer is formed on the insulating layer (S225). Steps S240 to S255 are repeated according to the number of necessary metal wiring layers.

The embodiment disclosed this time must be considered as illustrative in all points and not restrictive. For example, in the first and second embodiments, the evaluation of the SiO ₂ film formed on the silicon substrate has been described as an example, but the present invention is not limited to the above example. The present invention can be used for evaluating a semiconductor film or an insulating film formed on a semiconductor substrate, and further for evaluating a semiconductor film or an insulating film formed on an insulating substrate or a metal plate. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  DESCRIPTION OF SYMBOLS 1 Evaluation apparatus, 10 Vacuum chamber, 12 Sample, 14 Sample stand, 16 X-ray, 18 X-ray source, 20 Photoelectron, 22 Electron spectrometer, 24 Irradiation light, 26 Variable wavelength light source, 28 Control part.

Claims (5)

A first detection step of detecting temporal changes in the energy distribution of photoelectrons emitted from the semiconductor or insulator by irradiating the semiconductor or insulator on the sample surface with X-rays;
A second detection step for detecting a temporal change in the energy distribution of the photoelectrons generated by irradiating the sample surface with monochromatic light having an energy smaller than the band gap of the semiconductor or insulator in addition to the X-ray;
And evaluating a defect inside the semiconductor or the insulator based on the detection results of the first and second detection steps.   The evaluation method according to claim 1, wherein in the second detection step, a temporal change in the energy distribution of the photoelectrons is detected while gradually increasing the energy of the monochromatic light to be irradiated. The step of evaluating comprises
Obtaining a characteristic curve representing the relationship between the amount of shift of the energy value that gives the peak of the energy distribution of the photoelectrons detected in the first detection step and the X-ray irradiation time;
Separating the characteristic curve into a sum of one or more exponential curves;
The evaluation method according to claim 2, further comprising: detecting a change in one or more exponential function curves after the separation according to a step change in the energy of the monochromatic light in the second detection step. An X-ray source for irradiating the semiconductor or insulator on the sample surface with X-rays;
An electron spectrometer for detecting an energy distribution of photoelectrons emitted from the semiconductor or insulator by irradiation of the X-ray source;
A wavelength tunable light source for irradiating the sample surface with monochromatic light having an energy smaller than the band gap of the semiconductor or insulator;
A control unit,
The controller is
Detecting a first temporal change in the energy distribution of the photoelectrons detected when the sample surface is irradiated with X-rays by the X-ray source;
In addition to the X-ray, a second temporal change in the energy distribution of the photoelectrons detected when the monochromatic light is irradiated by the wavelength tunable light source is detected.
An evaluation apparatus configured to evaluate defects inside the semiconductor or the insulator based on the first and second temporal changes. Forming an insulating film on the semiconductor substrate;
A method for manufacturing a semiconductor device, comprising: evaluating the insulating film by the evaluation method according to claim 1.

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