EP2179268A2 - Procédé de détermination in-situ de la composition matérielle de couches minces optiques, dispositions pour mettre en uvre et utiliser ce procédé - Google Patents

Procédé de détermination in-situ de la composition matérielle de couches minces optiques, dispositions pour mettre en uvre et utiliser ce procédé

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Publication number
EP2179268A2
EP2179268A2 EP08784316A EP08784316A EP2179268A2 EP 2179268 A2 EP2179268 A2 EP 2179268A2 EP 08784316 A EP08784316 A EP 08784316A EP 08784316 A EP08784316 A EP 08784316A EP 2179268 A2 EP2179268 A2 EP 2179268A2
Authority
EP
European Patent Office
Prior art keywords
layer
optical
deposited
substrate
reflection
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP08784316A
Other languages
German (de)
English (en)
Inventor
Raik Hesse
Hans-Werner Schock
Daniel Abou-Ras
Thomas Unold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
Original Assignee
Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH filed Critical Helmholtz Zentrum Berlin fuer Materialien und Energie GmbH
Publication of EP2179268A2 publication Critical patent/EP2179268A2/fr
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00—Measuring arrangements characterised by the use of optical techniques
    • G01B11/02—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0616—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating
    • G01B11/0625—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating with measurement of absorption or reflection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00—Measuring arrangements characterised by the use of optical techniques
    • G01B11/02—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0616—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating
    • G01B11/0683—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating measurement during deposition or removal of the layer
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
    • G01N21/45—Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/8422—Investigating thin films, e.g. matrix isolation method

Definitions

  • the invention relates to a method for in-situ determination of the material composition of vapor deposited on a substrate optically thin layers having a interferometrically evaluable correlation between the optical layer parameters (complex refractive index n kO mpiex with real part: refractive index n Sc hic ht and imaginary parts: absorption coefficient ⁇ Sc hicht and real layer thickness d Sch ic ht), as well as arrangements for carrying out the method and applications.
  • the optical layer parameters complex refractive index n kO mpiex with real part: refractive index n Sc hic ht and imaginary parts: absorption coefficient ⁇ Sc hicht and real layer thickness d Sch ic ht
  • DE 197 23 729 A1 discloses a method for in-situ determination of optical layer constants in plasma and ion beam assisted etching and coating.
  • a method for determining optical constants from the reflection of light caused by the self-radiation of the surface processing sources will be described.
  • the spectra of the reflections are recorded from interferences that occur.
  • Four different wavelengths are individually detected via a wavelength filter. From the measured signals of the normalized radiation, the absolute (real) thickness of the layer is determined.
  • this method can only be used in systems with a plasma or an ion beam for surface treatment, since the intensity of the plasma or the ion beam must be additionally recorded. The substrate itself is not measured.
  • EP 1 435517 A1 describes the use of spectroscopic ellipsometers for the determination of thin multilayer systems.
  • ellipsometry only works reliably with very smooth layers.
  • an ellipsometric measurement is possible only ex-situ, since the reflection must be evaluated by a polarization measurement method. The evaluation is carried out by changing the polarization of the incident light and the resulting influence on the reflected radiation. The determination of the complex refractive index is effected by a defined wavelength change.
  • the method works for multilayer systems with an optical model, but which is based on the numerical adaptation (fitting) of a frequency-dependent function of thickness and refractive index (similar to FFT, Fast Fourier Transformation).
  • EP 1 467 177 A1 likewise discloses a thickness measuring method for multilayer systems. This method is based on an ex-situ measurement, which is followed by an evaluation due to a Fourier transformation. Light is radiated onto the sample and a frequency spectrum is created by the FFT. By evaluating the peaks of the FFT, the individual layers are determined in their thickness. A CCD (Charged Coupled Device) is used as a spatially resolving optical detector for different wavelengths.
  • CCD Charged Device
  • Reflections of optical radiation on smooth surfaces All methods are based on the measurement of total reflection and thus require one Normalization either by measuring the reference light or by subsequent measurement of refractive indices by other methods. Used optical models are based on the use of Fresnel equations. No method is used to control an evaporation process of materials to obtain an optically thin layer.
  • a method for deposition processes of chalcopyrite thin films on moving substrates is known, for example, from DE 102 56 909 B3.
  • a laser of coherent light of a wavelength is directed to a moving substrate to control the process of deposition and formation of a chalcopyrite thin film.
  • the control in this method is based on the scattering of laser light on rough surfaces.
  • the process of vapor deposition of Cu (In, Ga) Se 2 layers is divided into three stages. Stage I involves the evaporation of indium and gallium (co-evaporation or sequential evaporation), stage II the co-evaporation of copper and stage III the co-evaporation of indium and gallium. During the entire process selenium is evaporated.
  • the substrate is described comprehensively in material (glass, titanium or plastics) and properties. Different concepts of substrate movement are shown (run, rotation, roll-to-roll). Concepts for moving the laser used are given.
  • the process control in the known method is based on laser light scattering (LLS) and uses individual characteristic points. The scattered signals of the laser light are logged during the individual stages. In particular, the second stage leakage signals are used to estimate stoichiometric ratios in the deposited layer.
  • LLS laser light scattering
  • this control does not offer the possibility of carrying out a process in a reproducible manner since this requires a control with a numerical value assignment of the optical layer parameters.
  • Sakurai et al. known in-situ diagnostic methods for thin-film fabrication: utilization of heat radiation and light scattering (Progress in Photovoltaics: Research and Applications 12 (2004), pp. 219-234), of which the present invention as closest state of the
  • process control is not discussed, and the numerical values of the optical layer parameters are unknown, so that no quantitative control of the growth of thin layers and thus control of the actual values of the controlled variables (optical layer parameters) to the setpoints by adjusting the manipulated variables (process parameters ) can be made.
  • the TASK for the present invention is to be developed, the above-mentioned, generic method for in situ determination of the composition of material deposited from the vapor phase on a substrate optically thin layers with an interferometrically evaluable correlation between the optical layer parameters so that the material composition of the deposited layer can be determined with knowledge of the optical layer parameters.
  • the process should be cost-effective and immune to interference in real time feasible.
  • a preferred arrangement for carrying out the method should have corresponding components.
  • optically thin layers are those layers in which the complex refractive index nk o mpi e x (Real part: refractive index n SC hicht; imaginary: absorption coefficient ⁇ Sc hi ch t) and the real coating thickness dsohicw) in an interferometrically evaluated correlation are dependent on each other.
  • the limit of interferometry is reached when the layer is too thick or too high absorbing.
  • optical layers exhibit a thickness up to a maximum of the "l Ofachen the irradiated wavelength or a thickness of less than 1000 nm.
  • the method according to the invention comprises at least the following method steps:
  • the substrate on the deposition side is irradiated with incoherent light in the visible optical range.
  • light is directed at least three different wavelengths ⁇ i, X 2 , ⁇ 3 onto the deposited layer.
  • Three different wavelengths are required because three unknown optical layer parameters (refractive index nsc Wc ht, absorption coefficient ⁇ s Ch i cht and layer thickness d) are also to be determined.
  • Incoherent light can be used on both rough and smooth surfaces. The use of coherent light is limited to rough surfaces.
  • the diffuse or direct light scattering emanating from the deposited layer is detected optically spatially resolved in the three different wavelengths ⁇ -i, ⁇ 2, ⁇ 3 .
  • the time-dependent course of the reflection intensity R is measured in each case.
  • the light is radiated in such a way that no total reflection results. Total absorption also does not occur with optically thin layers.
  • each deposited layer is interpreted as an electromagnetic conductor with a variable field wave resistance Z G , a propagation constant ⁇ and a real layer thickness equivalent to the conductor length dschicw.
  • the optical layer model is numerically evaluated for the different wavelengths ⁇ -i, ⁇ 2 , ⁇ 3 . It will become apparent by numerical adaptation of the layer model or this function describing the time course of the detected reflection intensities, the real values for the optical layer parameters (refractive index n SCh i CHT, absorption coefficient K harsh, real layer thickness d Sc hich t) of the deposited layer. In this case, the wavelength-independent real layer thickness dschic h t is determined to the reference value, so that the inventive method is self-referencing. A reference formation from the outside with additional quantities to be detected, as known from the prior art, is eliminated.
  • the actual material composition of the detected deposited layer is then determined from the numerically determined values for the optical layer parameters. This is done by comparison with standard values of values for optical layer parameters of known material compositions.
  • the method according to the invention when changing the material composition between different layers, the determined values of the optical layer parameters of the previous layer are stored and used as reference values for a next layer. Therefore, the method according to the invention can also be used for any stack of optically thin layers, because it always analyzes the uppermost layer with respect to the underlying layers as a reference. Furthermore, it may be advantageous to additionally measure the reflection intensity which is caused by incident coherent light of a single wavelength (LLS). In this way, the influence of the surface roughness of the deposited layer can be taken into account. This requires, however, that a rough surface is present. Smooth surfaces can not be analyzed with coherent light.
  • LLS single wavelength
  • an optical imaging device such as a CCD or CMOS camera for the colors red, blue and green, as an optical detector and a White light source, can be found in the special execution part.
  • a preferred application of the method according to the invention consists in an embodiment as an in-situ process control in the production of vapor phase deposited on a substrate optically thin layers.
  • the method is incorporated into a control loop, with which the calculated actual values of the optical layer parameters of the optically thin
  • Layers are controlled as controlled variables to predetermined setpoint values by adaptation of the production parameters as manipulated variables in accordance with the determined actual values for the optical layer parameters.
  • the process according to the invention can still be used as an in-situ process control even if no optically thin layers, but absorbent layers are grown.
  • the method according to the invention is used at least for the estimation of the stoichiometry.
  • the reflection intensity R of the diffuse or direct light scattering emanating from the layer deposited on the substrate outside of the total reflection in at least two wavelengths ⁇ -i, ⁇ 2 is interpreted accordingly.
  • a significant change in the course indicates the point of stoichiometry achieved.
  • a simultaneous temperature monitoring of the evaporation sources via the spatially resolved optical detection by interpretation of the occurring color values of the temperature radiation of the evaporation sources done.
  • FIG. 1 A diagram for the transfer of conduction theory into optically thin layers
  • FIG. 1 B schematic diagram for interferometry on optically thin layers
  • FIGURE 2 Representation of the conversion of the time dependence of
  • FIGURES 3A-D Diagrams of fitted reflection in the deposition process
  • FIGURE 4 Diagram showing the measurement signals of all three
  • FIG. 5 process sketch for an entire PVD process
  • FIGURE 6 stacks of deposited optically thin layers for the entire PVD process
  • FIG. 7 SEM image of a stack of several layers
  • FIG. 8 sketch for an arrangement for a complete PVD process
  • FIG. 9 control loop for process control
  • FIG. 10 Measurement signals of a CCD detector (stage I)
  • FIG. 11 Diagram of the temporal intensity profile of the reflections
  • FIG. 12 Measurement signals of a CCD detector (stage II), FIG.
  • FIG. 13 Diagram for the temporal intensity profile of the reflections
  • FIGURE 14 Comparison of measurement signals invention / prior art and
  • FIG. 15 Comparison of measurement signals on rough layers between coherent and incoherent light sources.
  • the approach to the development of the method according to the invention is in the wave theory.
  • This theory describes the propagation of waves in dielectric media and is known, for example, in the field of high-frequency technology.
  • the wave theory is transferred to optically thin layers.
  • Each layer is interpreted as a single line with a parameter set of propagation constant, field wave resistance and thickness (corresponds to the conductor length) and clearly described (see FIG. 1A).
  • two optically thin layers are represented by two characteristic impedances ZF1, ZF2 and the thickness d of the just growing, upper layer.
  • the field wave resistance Z F is defined by the dielectric in which the shaft is located.
  • a material can be clearly described by the permeability ⁇ and the permittivity ⁇ .
  • the field wave resistance ZF can be defined according to equation (1).
  • the field resistance ZF according to another notation for the field resistance ZF also applies:
  • n is the (real) refractive index and K is the extinction coefficient (imaginary refractive index).
  • ZF 0 here is the characteristic impedance of the vacuum and a natural constant.
  • the origin of the equation is the telegraph equation (general form of the wave equation).
  • FIG. 1B shows the interferometry on optical thin layers with the sheet resistances ZF-i, ZF 2 (optically thin layers) and ZF 3 (substrate, in the selected exemplary embodiment made of molybdenum) compared with air ("air") (Layer thickness 20 - 30 nm) consists of a compound of the evaporated selenium with the molybdenum of the substrate, the next layer consists of a compound of gallium and selenium.
  • the layer thickness ⁇ d at known temperature of the evaporation sources
  • the refractive index n real part
  • n real part
  • the absorption coefficient K imaging part
  • the reflection intensity R of the incident light radiation can be calculated by the layer system. It applies with Z F o as the field wave resistance of the vacuum:
  • Y propagation constant
  • the calculation unit performs the calculations of equations (2) and (3) in-situ to determine the thickness and the complex refractive index.
  • the measurement signals of the optical detector in the three different wavelengths are numerically adapted ("fitted" by using varied values for complex refractive index and layer thickness) with the optical layer model and compared with results of formulas 2 and 3.
  • Preliminary remark The use of three wavelengths ⁇ -i, X 2 , ⁇ 3 is necessary for the method according to the invention.
  • the reason for this lies in the missing reference size of the incident light.
  • the light usually enters the evaporation chamber via a disk, which is regularly involuntarily co-evaporated.
  • the knowledge of the intensity of the radiation source is of no use, since a vaporized disc through which the light passes through greatly influences the characteristic of the light. In the measurement of the reflection, therefore, a different reference had to be found in the invention.
  • One of the three unknown quantities should serve as a reference.
  • the complex refractive index is wavelength-dependent and therefore can not be used.
  • the thickness is not wavelength dependent and can therefore be used as a reference since it must be identical for all measured wavelengths.
  • the method according to the invention can therefore be termed "self-referencing".
  • the starting point of the calculation for the method according to the invention is the measurement of the reflection intensity in three different wavelengths Xu X 2 , ⁇ 3 .
  • a CCD Charged Coupled Device
  • the reflection intensity R for three wavelengths ⁇ -i, X 2, ⁇ 3 (red, green and blue) is present through the CCD and evaluated individually
  • the conversion from time to thickness is done at the beginning of the deposition process on the basis of the occurring interference maxima.
  • the calculated thickness is the optical thickness d opt , ie it remains the previously unknown Refractive index in thickness initially included.
  • ⁇ is the angle of incidence
  • ⁇ the wavelength of the incident light
  • the optical layer thickness d opt is calculated as half the wavelength XR of the time course of the reflection intensity
  • FIG. 2 shows a diagram for converting the time dependence of the reflection intensity R (ordinate: RGB signal, abscissa: time / time in any unit) into the thickness dependence.
  • the reflection intensity can be defined by means of the characteristic impedance according to equation (3).
  • the characteristic impedance of the vacuum Z F0 is known and thus can be taken into account by changing the equation 3, the total resistance Z G of the vapor-deposited layer.
  • the resistor Z G describes the vapor-deposited layer and the underlying substrate. In order to separate the two layers from each other, equation (2) is still applied considering equation (4).
  • a fit compares the equation (2) with the measured reflection intensities. In this case, a determination of the measured values is carried out individually for all three measured wavelengths by the fit of equation (2).
  • the real thickness d is calculated numerically, with the thickness of the deposited layer for all three
  • Wavelengths must have the same value.
  • Equation (2) For each of the wavelengths, using the calculated thickness of step 1, equation (2) is solved.
  • the reflection measurement of each wavelength is fitted with Equation (5) and Equation (2).
  • Errors are determined by the real thickness and refractive index. III) For the entire process, repeat steps 1 and 2 until the limit of interferometry is reached (layer too thick or too high absorbing).
  • FIG. 3A shows the applied reflection (solid line) to the measured reflection intensity values (+) of Ga 2 Se 3 for a deposition process (ordinate: RGB signal, abscissa: time / time in arbitrary unit).
  • FIG. 3B shows by way of example how the method according to the invention operates.
  • the Fit the optical layer model
  • the Fit runs along and calculates the thickness and the complex refractive index during the process. While the thickness in Figure 3B is visibly juxtaposed as the axis of time, the measurement of the complex refractive index is not visibly included.
  • FIG. 3C shows the temporal
  • the FIGURE 3D shows the corresponding temporal intensity course of the red (circles) and the blue (squares) reflections in stage I. Shown is also the occurring absorption by the deposited layer by a corresponding simulation of the curve envelope.
  • the calculated optical layer parameters result in a proportion Ga / III of 0.5028 as a proportion Ga to the proportion In + Ga (Ga / Ga + In).
  • the composition of this layer is known and can be taken into account accordingly.
  • the routine shown is performed for all three wavelengths.
  • stage I sequential vaporization of gallium (in gallium zero, indium is evaporated, permanent evaporation of selenium) shows FIGURE 4 (ordinate: RGB signal, abscissa: time / time in any unit) simultaneously all three evaluated wavelengths.
  • the triangles show the evaluation of the blue wavelength, the squares of the green wavelengths and the circles of the red wavelength.
  • the embodiment of the method according to the invention relates to the sequential co-vapor deposition of metals and non-metallic elements of the fifth to seventh main group, wherein there is at least one sequence of evaporation.
  • a possible timing of the evaporation for the elements A (eg In), B (eg Ga), C (eg Cu) and D (eg Se) can be seen in FIG.
  • the process described here is a sequential co-evaporation of the type Ga + Se, followed by In + Se, to obtain a layer stack of Ga 2 Se 3 and ln 2 S ⁇ 3 .
  • the stack of optically thin layers that can be generated by this evaporation process in stage I is shown schematically in FIG.
  • FIG. 7 A high-resolution SEM image of a complex stack made up of a plurality of superimposed, optically thin layers produced by the process control according to the invention is shown in FIG. 7.
  • the method according to the invention can always use the respectively uppermost deposited layer with respect to the underlying layers be analyzed as a reference layer in terms of their material composition. Therefore, the method is also applicable to stacks with any number of individual layers.
  • step II of the above process an absorbing Cu-containing layer is produced, to which interferometry is not applicable.
  • the method according to the invention can be used to estimate the stoichiometry.
  • stage III then again analyzable optically thin layers are deposited.
  • FIG. 8 shows the basic structure of an arrangement for carrying out the method according to the invention.
  • the elements A, B, C, D are evaporated sequentially and deposit on the deposition side of the substrate S rotating in the embodiment as composite layers.
  • the depositing layers reflect incident light as diffuse or direct reflections of incoherent radiation (no total reflection).
  • the diffuse or direct reflections with at least one spatially resolving optical detector D! added.
  • Another detector D2 may be provided, for example, orthogonal to the first detector D1 laterally from the substrate S.
  • the optical radiation interacts with the vapor-deposited optically thin layer in a characteristic manner, so that from the reflection with the detectors D1, D2, the quality of the vapor-deposited layer can be assessed directly with respect to its composition and any deficiencies in the control loop can be used to correct the process.
  • the evaporation sources A, B, C, D, X, Y are simultaneously used as incoherent light sources ILQ in order to irradiate light of different wavelengths onto the deposition side of the substrate S.
  • white light sources ILQ (without evaporator function) with an infinite wavelength spectrum can also be used.
  • a coherent light source KLQ (here a laser) may be provided in order to be able to take into account the influence of the surface roughness of the depositing layers.
  • evaporation sources X, Y for example, for the evaporation of non-metallic elements, be provided.
  • the control of Koverdampfens requires no spatial separation of the individual evaporation sequences, but it does not exclude them.
  • Essential for the regulation of the vapor deposition process is the reflection measurement and evaluation of the incident on the moving substrate optical radiation.
  • the radiation must be spatially separated from each other in order to evaluate the individual radiations in the system can.
  • the spatial resolution optical detector D for example a CCD camera equipped with optical instruments, is mounted inside or outside the PVD chamber PVD.
  • a corresponding window F is provided in the chamber wall, which is also occupied during the evaporation process with a Abscheide für so that an external referencing of the control system is not possible. This is also not required in the method according to the invention by its self-referencing capability.
  • the CCD cameras convert optical radiation received by means of an array of optical sensors into color values in the wavelength range from 400 nm to 700 nm. These then correspond to the incident wavelength and have been calculated with the spectral sensitivity of the individual sensors of the CCD chip.
  • a CCD camera consists of an array of optical sensors and can thereby locally separate the incident signals.
  • the use of CCD cameras does not limit the type of optical radiation. Rather, it can be used for monitoring any optical radiation in the visible spectrum. Furthermore, the number and location of the CCD cameras are arbitrary and can be freely selected due to the quality of the cameras used.
  • the general control of moving or unmoving substrates in connection with a spatially resolved optical detection is also solved particularly elegantly by the use of a CCD camera, which is aligned with its optics in the direction of the substrate.
  • the method according to the invention can be used as a process control for an evaporation process of the type described above.
  • a quantitative control of the process by influencing the process parameters is possible.
  • this regulation differs significantly from the known regulations in this field, with which only a qualitative control (according to predetermined characteristic points) is possible without precise numerical knowledge of the optical layer parameters.
  • the function of the associated control circuit is indicated schematically in FIG. 9 for the general case (cf. FIG. 8).
  • the detectors D1 and D2 serve to measure the reflection intensities and transmit the measurement signal to the control unit CU.
  • the control unit CU uses the measured signals using the type of light sources used for control (ILQ, KLQ). Here, the operation of the light sources is freely selectable. These may be chopped or choppy light signals. From the measured signals correlated to the light sources used, the control unit controls the movement of the substrate S, as well as the evaporation sources A 1 B 1 C 1 D 1 X 1 Y (X, Y may be non-metallic evaporation sources, for example).
  • FIG. 10 shows, by way of example, the measurement signal of an optical CCD detector with visible reflections of the light sources and the temperatures of the evaporation sources for stage I of the exemplarily selected 3-stage vapor deposition process of Cu (In, Ga) Se 2 thin films.
  • the CCD camera is located in the bottom of the PVD chamber and is oriented with its optics perpendicular in the direction of the substrate S (see FIG. 8).
  • the possibility of monitoring the function of the evaporation sources by estimating their temperature via the control unit CU is simultaneously given by the use of a CCD camera.
  • the colors of the original measurement protocol are reproduced only by their gray value.
  • the original measurement protocol shows a red reflection of the light sources Ac and B 1 a green reflection of the light sources A B and the evaporation sources B and X as well as external noise and a blue reflection at the evaporator sources A and C (with red islands). While the evaporation sources A and B have approximately the same temperature and thus have a similar temperature radiation, distribution and color, the evaporation source C is operated at a significantly higher temperature.
  • the higher temperature is represented by the CCD camera as blue color. If used incorrectly, the source of evaporation might not turn blue, but would not be visible.
  • the evaporation source C Due to the high temperature, it has intense dots measured by colors other than blue within the temperature distribution.
  • the CCD camera is adapted to the human eye, displaying areas of highest intensity as green, as the human eye has the highest sensitivity to green.
  • FIG. 10 shows the reflections of the individual light sources (also evaporation sources).
  • the measurement signals For use as a measurement signal for a control loop, the measurement signals must first be evaluated by the control unit CU for semitransparent, optically thin layers.
  • the CCD camera separates the reflections locally from each other and thus enables a separate evaluation within the control unit.
  • the control unit then converts the measured, separate reflection intensities of the individual light sources into numerical intensities and applies them in a time-dependent manner.
  • FIG. 11 shows the time profile of the locally separated reflection intensities processed by the control unit at the substrate surface (red-green-blue intensity "RGB intensity” in any unit (au) over the time "time”).
  • the wavelengths of light sources A and B are indicated by their wavelength.
  • a laser module was used as light source B.
  • the light source A is due to the temperature radiation of the source A (here: gallium melt). From the physical laws that are well known for the determination of an optically thin layer, it is possible with two different wavelengths to determine the thickness of the resulting layer as well as the complex refractive index (two components) of the deposited layer (see above).
  • the control unit has data on the expected layer on the substrate and, with the aid of these data, which are in the form of step diagrams and values for the wavelength-dependent complex refractive index, determines the optical layer parameters and, depending thereon, the layer composition of the substance formed.
  • the control unit provides the information that the deposited layer is Ga 2 Se 3 . This substance has a refractive index of 2.4 and absorbs only at a wavelength below 580nm.
  • the method according to the invention is limited only by the thickness of the deposited layer, since from a thickness of about ten times the wavelength of the incident radiation the interferometry provides no longer valid results.
  • this limitation is not achieved by restricting the invention to optically thin layers and is therefore negligible.
  • the method according to the invention in an embodiment according to FIG. 8 provides for the interferometric calculations a sufficient control possibility and can thus be used for the purpose of a process control.
  • at least one stoichiometric estimate can be carried out due to the special optical evaluation for absorbing layers. Such an estimate is also known for example from DE 102 56 909 B3.
  • step I a semitransparent layer of indium, gallium and selenium was deposited on the substrate.
  • FIG. 12 shows the measurement signal of the CCD camera for the evaporation of copper in stage II on the semitransparent layer just described. It becomes an exemplary measurement signal of the detector with visible reflection of Light sources, and the temperature of the evaporation sources for stage Il shown.
  • FIGURE 12 shows the recorded area of the CCD camera used to control the process.
  • the interference signal of an external radiation has been cut out here, which can be achieved by the spatial resolution of the measurement signal.
  • the rotation causes a partial overlap of the two light sources A and B.
  • the control unit is able to separate both reflections and to evaluate them individually.
  • the said reflection of the light source B corresponds to the already described exemplary light source for the temperature estimation of the evaporation sources for proof of function.
  • the aim of this exemplary process is the estimation of the stoichiometry in the molar amount of the metals indium and gallium and the metal copper.
  • the amounts of indium and gallium should correspond to the amount of copper on the substrate.
  • the control unit is due to the target composition for this Substance calibrated and can thus carry out the estimation of the stoichiometry.
  • the CCD camera measures the process until the processed measurement signals in the control unit detect the occurrence of a copper selenide (Cu 2-x Se) coating on the surface of the deposited layer. For a CCD camera, this effect is evidenced by the continuous increase in the intensity of the reflection of the light source Ac with the simultaneous occurrence of a decrease in the reflected light source B in the exemplary system.
  • FIG. 13 shows the time profile of the CCD camera measurement (red-green-blue intensity "RGB intensity” in arbitrary units (a.u.) over time "time”) evaluated by the control unit.
  • the course of the temperature reflection of the copper source (upper curve, color green, “Intensity from Lightsource A”) is shown together with the reflection of the light source B (here: laser 635 nm wavelength, lower curve, color red, Intensity from Lightsource B ”) ,
  • the behavior described is indicated by the oval (“approximation of stoichiometry”) in FIGURE 13. The occurrence of this behavior satisfies the requirement for an estimation of the stoichiometry within the deposited layer.
  • the evaluations of the control unit are compared with those of the control system according to DE 102 56 909 B3.
  • a photodiode followed by a lock-in amplifier is used.
  • the photodiode receives a modulated reflected signal from the substrate surface, integrates the entire signal, and extracts the modulated signal for analysis.
  • a qualitative control with the known method according to DE 102 56 909 B3 is possible on the basis of characteristic individual points.
  • FIG. 14 shows a comparison between the two methods in the time course of the entire control process according to the invention (red-green-blue intensity "RGB intensity".
  • the lower, light gray curve in step 1 shows the time course of the reflection intensity of the color green (from the RGB
  • the average, thin black curve shows in comparison the signal profile from the method according to DE 102 56 909 B3 a very similar result can be seen in the measurements (compare upper two curves)
  • the lower curve for the method according to the invention shows the general insensitivity of the laser signal to a relatively smooth substrate / layer during stage I.
  • the measurement according to DE 102 56 909 B3 is highly prone to error as the process has to be rough-layered
  • One of the problems is that laser signals, ie coherent beams Due to the roughness of the surface is influenced more than incoherent radiation.
  • a quantitative control of the layer deposition is not possible with the known method according to DE 102 56 909 B3, since the measured interferences are superimposed on the roughness of the deposited layer. Since the availability of incoherent light means that this dependence does not occur in the method according to the invention, the corresponding control system with the CCD camera offers the possibility of characterizing the deposited layer by a numerical determination of the thickness and determination of the refractive index. For stage II, a clear occurrence of the stoichiometry can be observed with both systems, which, however, is represented differently. For the stage III, not further shown in FIG. 14, a quantitative analysis of the layer composition could again be produced with the method according to the invention.
  • FIGURE 15 shows a comparison of coherent and incoherent light sources on rough substrates.
  • a simultaneous measurement is shown between the method according to the invention and the method according to DE 102 56 909 B3 (LLS).
  • LLS liquid crystal display
  • the measurement signal of the LLS shows a very weak signal, while the signals of the method according to the invention are clearly visible.
  • the influence of the roughness on the laser signal is again indicated by arrows.
  • An apparent phase shift of the reflection signals of the LLS does not allow an accurate measurement, whereas the method according to the invention with white light sources shows no phase shift.
  • sources of evaporation A 1 B 1 C 1 D 1 X 1 Y are sources of evaporation for any elements - A 1 B 1 C 1 D: any metals, X 1 Y: any non-metallic elements of the V. Vll, -Hauptrete.
  • the named light sources A, B are light sources of any nature a.
  • Coherent sources lasers of any nature (e.g., gas discharge lasers,
  • Monochromatic, non-coherent light eg light emitting diodes of any optical wavelength, division of continuous optical spectra by optical methods, eg monochromators, filters
  • Non-monochromatic, non-coherent light eg: white light sources, such as halogen lamps D.
  • Other light sources eg: optical radiation of metal melts, the melts produced in the sources A, B, C, D and optical radiation of melts of the described sources X 1 Y).
  • the positioning of the designated light sources A, B can take place a.) Within the process device at any angle ⁇ b.) Outside the process device at any angle ⁇ using heated or unheated optically transparent devices (eg windows)
  • the coupling of the radiation of the designated light sources A 1 B can take place by a.) Direct illumination of the substrate during the deposition process to be controlled with II. Named light sources without optical instruments b.) Direct illumination of the substrate during the controlled vapor deposition with after II. Named light sources with any optical instruments connected upstream (eg linear and circular polarizers, convex and concave lenses for imaging, interference filters or other filters for wavelength adjustment of the light sources) c.) Direct illumination of the substrate during the vapor deposition process to be controlled with light sources named after II by guiding the optical radiation by means of light guides (eg: optical mono- and multimode fibers, mirror systems for deflecting the optical radiation and adjusting the position and the angle of incidence on the substrate)
  • light guides eg: optical mono- and multimode fibers, mirror systems for deflecting the optical radiation and adjusting the position and the angle of incidence on the substrate
  • the named detectors are spatially resolving, optical sensors of any nature in the formation of a.) Integrating, spatially resolving detectors without optical instruments (eg: photodiode arrays or arrays, line and line CCDs, which are suitable for the measurement of optical radiation, arrangements of several locally separated photodiodes) b.) integrating, spatially resolving detectors with optical instruments (eg named elements according to Va) with imaging convex or concave lenses, interference filters or other filters for adjusting the sensitivity to specific wavelengths, decomposition of optical signals with monochromatic prisms or C) non-integrating, spatially resolving detectors without optical Instruments (eg CCD cameras of various resolution and design, photographic plates, photosensitive papers (films), camera systems for imaging) d.) Non-integrating, spatially resolving detectors with optical instruments according to Vc) (eg cameras with optical imaging)
  • optical instruments eg: photodiode arrays or arrays, line and line CCDs, which
  • the named substrate is of any nature (e.g., metal foils, sheets of glass, plastic sheeting; the substrates may be electroconductive materials such as molybdenum, and suitable materials to aid in the development of the substrate
  • the movement of said substrate is of any nature (e.g., rotation, linear motion in the vertical and horizontal directions and any combination of the two aforementioned movements, substrate standstill is included).
  • the layer to be deposited during the evaporation process is of any nature and can be applied to a.)
  • Obtaining an absorber layer for use in photovoltaic applications eg: in thin film solar cells of the structure ABCXY2, such as and the structure A 2 (BC) x Di -x (XyY-yy) 4 , such as
  • control system for the use of the control system is of any nature and can serve for a.) Control of a sequential one-stage or multi-stage system which evaporates per sequence at least one metal and one non-metal according to I. to obtain optically thin layers according to VIII. Vapor deposition (physical vapor deposition - PVD), b.) Control of a thermal process, which performs the method of Vlll.d.),
  • the control unit of the control system makes use of the digital and analog read-in of imaging and integrating methods with instruments to V. Processing of the read measuring signals by means of digital technologies (eg: computer) and regulating signals from the control unit are using digital technologies the systems to be controlled according to I, VII transferred. A.) Evaluation of the measuring signals with detectors according to V., b.) Control of the temperature of the sources according to I., of the substrate according to VI. and the movement of the substrate according to VII.
  • control unit is of any nature and suitable for a.) In-situ control of continuous processes according to IX for obtaining optically thin layers according to VIII and b.) In-situ control of sequential processes according to IX for obtaining optically thin layers VIII.

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Abstract

Les procédés connus sont fondés sur la mesure de la réflexion totale et analysent les réflexions d'un rayonnement optique pour des surfaces lisses. Ils ont ainsi besoin d'un étalonnage par mesure sur la lumière de référence, ou d'une autre mesure de l'indice de réfraction. Ils ne sont donc pas universellement utilisables, en particulier pour le contrôle des processus de vaporisation. Les procédés de contrôle connus dans ce domaine ne travaillent que qualitativement, en s'appuyant sur des caractéristiques spécifiques du processus de fabrication. Pour assurer une véritable régulation quantitative, il est donc essentiel de rendre également mesurables les composants à réguler (paramètres de couche optique). Le procédé conforme à l'invention détermine directement la composition matérielle de couches minces optiques, et se fonde sur un modèle de couche optique qui a été déduit de la théorie de la conduction électromagnétique à l'aide des impédances de champs. La couche isolée est exposée, de préférence, à une lumière spectrale non cohérente, de préférence celle d'une source de lumière blanche. Les intensités de réflexion en dehors de la réflexion totale sont déterminées au moyen d'un détecteur optique à résolution locale, de préférence un détecteur de type CCD, et vont alimenter le modèle de couche. Les fonctions caractéristiques du modèle de couche sont adaptées aux valeurs réelles de processus, et servent à déterminer les valeurs numériques des paramètres de couche optique, à partir desquels il est possible de déduire la composition matérielle concrète.
EP08784316A 2007-07-20 2008-07-09 Procédé de détermination in-situ de la composition matérielle de couches minces optiques, dispositions pour mettre en uvre et utiliser ce procédé Ceased EP2179268A2 (fr)

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DE102007034289A DE102007034289B3 (de) 2007-07-20 2007-07-20 Verfahren zur in-situ-Bestimmung der stofflichen Zusammensetzung von optisch dünnen Schichten, Anordnungen zur Durchführung und Anwendungen des Verfahrens
PCT/DE2008/001130 WO2009012748A2 (fr) 2007-07-20 2008-07-09 Procédé de détermination in-situ de la composition matérielle de couches minces optiques, dispositions pour mettre en œuvre et utiliser ce procédé

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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100053332A1 (en) * 2008-08-27 2010-03-04 Nova Research, Inc. Frustrated internal reflection uncooled infrared camera
TWI373851B (en) * 2008-11-25 2012-10-01 Nexpower Technology Corp Stacked-layered thin film solar cell and manufacturing method thereof
US20110299720A1 (en) * 2010-03-18 2011-12-08 The Regents Of The University Of California Systems and methods for material layer identification through image processing
CN103026191B (zh) 2010-07-21 2015-08-19 第一太阳能有限公司 温度调整光谱仪
TWI547683B (zh) * 2010-12-06 2016-09-01 Univ Nat Central Multi - wavelength optical measurement method for thin film elements
TWI426258B (zh) * 2010-12-06 2014-02-11 Univ Nat Central Real - time Monitoring of Film Growth by Dynamic Interferometer
MX359196B (es) * 2014-02-14 2018-09-19 Halliburton Energy Services Inc Espectroscopía in situ para el monitoreo de la fabricación de elementos computacionales integrados.
MX360069B (es) * 2014-04-24 2018-10-22 Halliburton Energy Services Inc Modificacion de las propiedades opticas de un elemento informatico integrado mediante implantacion de iones.
GB2529251A (en) * 2014-08-15 2016-02-17 Taylor Hobson Ltd Apparatus for and a method of determining a characteristic of a sample
DE102015115117B4 (de) 2015-07-31 2021-04-29 Helmholtz-Zentrum Berlin für Materialien und Energie Gesellschaft mit beschränkter Haftung Verfahren zur optischen in-situ-Kontrolle zumindest einer auf einem Substrat aufwachsenden Schicht aus Verbindungshalbleitern
US10234402B2 (en) 2017-01-05 2019-03-19 Kla-Tencor Corporation Systems and methods for defect material classification
WO2020005203A1 (fr) * 2018-06-25 2020-01-02 Halliburton Energy Services, Inc. Réglage de densité in situ pendant la fabrication de matériaux de film mince
CN115885372A (zh) * 2021-01-08 2023-03-31 朗姆研究公司 用于薄膜光学测量的系统和方法
CN114184624A (zh) * 2021-11-16 2022-03-15 厦门理工学院 一种透明介质薄层的缺陷检测方法和装置

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8304212A (nl) 1983-12-07 1984-10-01 Philips Nv Enkelvoudige collimatorlens met een asferisch oppervlak.
US5450250A (en) * 1992-02-28 1995-09-12 E-Systems, Inc. Method for transparently marking the location of data files on recording media
DE19518113A1 (de) 1995-05-17 1996-11-21 Siemens Ag Verfahren zur Bestimmung einer Störgrößenaufschaltung
WO1996036906A1 (fr) * 1995-05-19 1996-11-21 Keller Weingarten Ursula Composant optique pour la production d'un rayonnement laser pulse
DE19723729A1 (de) * 1997-06-01 1998-12-03 Heinrich Friedhelm Dr In-situ Bestimmung optischer Schichtkonstanten beim Plasma und Ionenstrahl-unterstützten Ätzen und Beschichten
US6242739B1 (en) * 1998-04-21 2001-06-05 Alexander P. Cherkassky Method and apparatus for non-destructive determination of film thickness and dopant concentration using fourier transform infrared spectrometry
JP2002005745A (ja) * 2000-06-26 2002-01-09 Nec Corp 温度測定装置、および温度測定方法
US6891627B1 (en) 2000-09-20 2005-05-10 Kla-Tencor Technologies Corp. Methods and systems for determining a critical dimension and overlay of a specimen
KR100892743B1 (ko) * 2001-09-06 2009-04-15 가부시키가이샤 호리바 세이사꾸쇼 분광타원계를 사용한 박막층 구조의 해석방법
US6815235B1 (en) 2002-11-25 2004-11-09 Advanced Micro Devices, Inc. Methods of controlling formation of metal silicide regions, and system for performing same
DE10256909B3 (de) * 2002-11-30 2004-07-29 Hahn-Meitner-Institut Berlin Gmbh Verfahren zur Herstellung einer Chalkogenid-Halbleiterschicht mit optischer in-situ-Prozesskontrolle und Vorrichtung zur Verfahrensdurchführung
EP1467177A1 (fr) * 2003-04-09 2004-10-13 Mitsubishi Chemical Engineering Corporation Procédé et appareil pour mesurer les épaisseurs de couches d'une structure multicouche
US7271896B2 (en) * 2003-12-29 2007-09-18 Intel Corporation Detection of biomolecules using porous biosensors and raman spectroscopy
DE102005023735A1 (de) * 2005-05-23 2006-11-30 Leica Microsystems Jena Gmbh Verfahren zur automatischen Durchführung einer Oberflächenuntersuchung
DE102005023737A1 (de) * 2005-05-23 2006-11-30 Leica Microsystems Jena Gmbh Verfahren zum Berechnen vieler Spektren der Totalreflexion
DE102006016132A1 (de) * 2005-09-22 2007-03-29 Robert Bosch Gmbh Interferometrische Messvorrichtung
CN100461343C (zh) * 2005-09-28 2009-02-11 中芯国际集成电路制造(上海)有限公司 用于半导体器件的使用预处理的材料原子层沉积的方法
DE102005050795A1 (de) * 2005-10-24 2007-04-26 Leopold Kostal Gmbh & Co. Kg Meßvorrichtung zur Bestimmung der Dicke und/oder der optischen Transmissionseigenschaften einer Scheibe, vorzugsweise einer Fahrzeugscheibe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009012748A2 *

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DE102007034289B3 (de) 2009-01-29
US8338194B2 (en) 2012-12-25
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US20100291714A1 (en) 2010-11-18
WO2009012748A2 (fr) 2009-01-29

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