JP2005134324A - Analytical method and quality control method for transparent conductive film, and solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an analytical method for a transparent conductive film capable of measuring a film thickness without using a light interference method, and capable of measuring easily a haze rate. <P>SOLUTION: White light is emitted from a line illuminator 3a toward a glass substrate 11 with the transparent conductive film, reflected light is dispersed spectrally into three wavelengths of R (red), G (green) and B (blue) by a color line sensor camera 2a, and light intensities of the wavelengths are computed to calculate the film thickness or the haze rate of the transparent conductive film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for analyzing a transparent conductive film formed on, for example, a glass substrate of a solar cell.

In solar cells and liquid crystal display devices, a transparent conductive film is formed on a transparent glass substrate. Such a transparent conductive film is quality controlled by measuring the film thickness (see Patent Document 1).
Moreover, quality control is made | formed by measuring the haze rate of the glass substrate in which the transparent conductive film was formed.

JP-A-9-133517 (paragraphs [0002] to [0009] and FIGS. 1 to 2)

  However, although the transparent conductive film depends on the film forming conditions, the transparent conductive film has a shape with unevenness on the surface. In particular, the transparent conductive film used in the solar cell is actively formed with irregularities on the surface for the purpose of confining light. As the degree of unevenness, for example, the unevenness is about 0.3 μm with respect to a film thickness of 0.8 μm. In such a transparent conductive film having a large degree of unevenness, there is a problem that even if light is irradiated for film thickness measurement, partial coherence occurs, light interference cannot be obtained, and the film thickness cannot be measured.

  On the other hand, the measurement of the haze ratio is generally performed by a commercially available haze meter, and it is difficult to incorporate the haze ratio into a production line because of the device configuration. In particular, a haze meter that measures a large-sized solar cell substrate of about 1 m square at a time is not commercially available, and in practice, it must be relied on a sampling inspection. In this case, there is a problem that the yield is lowered and the product cannot be guaranteed.

  The present invention has been made in view of the above circumstances, and provides a transparent conductive film analysis method and a transparent conductive film quality control method capable of measuring a film thickness without using an optical interference method and easily measuring a haze ratio. The purpose is to provide.

In order to solve the above problems, the present invention employs the following means.
That is, according to the transparent conductive film analyzing method according to the present invention, the transparent conductive film is irradiated with light, the reflected light is dispersed into at least two wavelengths, and the light intensity at these wavelengths is calculated to calculate the transparent conductive film. The film thickness of the film is calculated.

The inventors have found that a value obtained by calculating the intensity of reflected light of at least two different wavelengths has a strong correlation with the film thickness. As an arithmetic expression, for example, a value obtained by dividing the second strongest light intensity by the strongest light intensity is multiplied by the first constant, and the second constant is added thereto.
Thus, if the reflected light is obtained, the film thickness of the transparent conductive film can be calculated even if the light interference is not obtained.

  According to the transparent conductive film analysis method of the present invention, the transparent conductive film is irradiated with light, the reflected light is dispersed into at least two wavelengths, and the light intensity at these wavelengths is calculated to calculate the haze of the transparent conductive film. The rate is calculated.

The inventors have found that a value obtained by calculating the intensity of reflected light of at least two different wavelengths has a strong correlation with the haze ratio. As an arithmetic expression, for example, these intensities are linearly combined.
Thus, if the reflected light is obtained, the haze ratio of the transparent conductive film can be calculated without preparing a haze meter separately.

  According to the transparent conductive film analysis method of the present invention, the light applied to the transparent conductive film is white light, and the reflected light is split into three colors of red, green and blue.

If white light is used as the light applied to the transparent conductive film, a generally available inexpensive light source (such as a fluorescent lamp) can be used. And if it is white light, naturally it has the wavelength of red (R), green (G), and blue (B) which are the three primary colors of light. In order to split the reflected light of white light having the three primary colors of light into the three primary colors, a general color camera may be used.
Thus, the transparent conductive film analysis method of the present invention can be carried out with a simple configuration.

  The transparent conductive film quality control method of the present invention is characterized by managing the quality of the transparent conductive film using the transparent conductive film analysis method.

  The transparent conductive film analysis method according to the present invention can be realized by a simple optical system because the film thickness or haze ratio of the transparent conductive film can be calculated as long as reflected light is obtained. Therefore, an apparatus for realizing this analysis method can be easily incorporated into the transparent conductive film production line. As a result, 100% inspection of the transparent conductive film is possible, and quality control is performed extremely well.

  The solar cell of this invention is equipped with the glass substrate with a transparent conductive film quality-controlled by the said transparent conductive film quality control method, It is characterized by the above-mentioned.

Since the transparent conductive film used for the solar cell is provided with irregularities on the surface for the purpose of confining light, it is difficult to obtain light interference. If the transparent conductive film analysis method of the present invention is used, the film thickness or the haze ratio can be calculated as long as the reflected light is obtained, which is suitable for quality control of the transparent conductive film used in the solar cell.
In addition, since all the solar cells quality-controlled by the transparent conductive film quality control method according to the present invention can be inspected, the yield is improved and product guarantee is ensured.

  The transparent conductive film analyzer of the present invention includes a light irradiating means for irradiating light to the transparent conductive film, a spectroscopic means for splitting the light reflected by the transparent conductive film into at least two wavelengths, and the intensity of the split light. And calculating means for calculating the film thickness and / or haze ratio of the transparent conductive film.

Since the light reflected at the transparent conductive film is divided into at least two wavelengths and the film thickness or haze ratio of the transparent conductive film is calculated by calculating the light intensity of these wavelengths, only the reflected light can be obtained. The film thickness or haze ratio can be calculated even for a transparent conductive film in which unevenness is present on the surface and interference light cannot be obtained.
Thus, since the film thickness or haze ratio can be calculated by a simple optical system, it can be easily incorporated into the production line, and 100% inspection of the transparent conductive film becomes possible.

Embodiments according to the present invention will be described below with reference to the drawings.
In FIG. 1, the structure of the transparent conductive film analyzer 10 used for a solar cell panel is shown.
This transparent conductive film analyzer 10 has a transparent glass substrate of about 1 m square and a transparent conductive film (TCO: Transparent) made of ITO (Indium Tin Oxide), zinc oxide, tin oxide or the like.
A glass substrate 11 with a transparent conductive film on which Conductive Oxide) is formed is conveyed. This glass substrate 11 with a transparent conductive film is conveyed so that a transparent conductive film may become an upper surface. Note that an SiO ₂ film may be formed as a base film between the transparent conductive film and the glass substrate in order to prevent diffusion of alkali components from the glass substrate.
The transparent conductive film analyzer 10 includes a conveyor 1a, a color line sensor camera (spectral means) 2a, a line illuminator (light irradiating means) 3a, a dimmer 4a, a photoelectric switch 5a, a rotary encoder 6a, an image processing apparatus (calculation). Means) 7a and display device 8a are mainly provided.

  The conveyor 1a is provided with a plurality of rollers 1A-1, 1A-2,... For conveying the glass substrate 11 with a transparent conductive film. These rollers 1A-1, 1A-2,... Simultaneously rotate at a predetermined rotation speed in a predetermined direction, whereby the glass substrate 11 with a transparent conductive film is conveyed in the conveyance direction Y.

The color line sensor camera 2a and the line illuminator 3a are installed so as to be positioned above the conveyor 1a.
FIG. 2 shows the positional relationship between the color line sensor camera 2a and the line illuminator 3a.
The line illuminator 3a is a fluorescent light source and emits white light. The line illuminator 3a is configured to irradiate the sheet-shaped irradiation light L1, and on the surface of the glass substrate 11 with a transparent conductive film, a line shape (having a predetermined width) orthogonal to the traveling direction of the glass substrate 11. (Linear) having light. The irradiated light L1 is reflected by the glass substrate 11 with a transparent conductive film, and enters the color line sensor camera 2a as reflected light L2.

  Each of the angle α1 formed between the perpendicular line L3 and the irradiation light L1 and the angle α2 formed between the perpendicular line L3 and the reflected light L2 with respect to the transport conveyor 1a is 16 to 20 in consideration of imaging conditions for the glass substrate 11 with a transparent conductive film. It is set so that it is within the range of about °.

As shown in FIG. 1, when the color line sensor camera 2a receives the trigger signal T from the image processing device 7a, the color line sensor camera 2a recognizes the imaging region of the glass substrate 11 with a transparent conductive film, and images the recognized imaging region. Then, the panel image PS is generated, and the generated panel image PS is transmitted to the image processing device 7a. At this time, the color line sensor camera 2a splits the captured image information into the three primary colors of R (red), G (green), and B (blue) light, and uses the respective luminances as the panel image PS as the image processing device 7a. Send to.
By scanning the line-shaped irradiation region from the line illuminator 3a as the glass substrate with a transparent conductive film is transported, a panel image PS of the entire glass substrate 11 with the transparent conductive film is generated.
The dimmer 4a adjusts the intensity of the irradiation light L1 to be a predetermined intensity.

  The photoelectric switch 5a detects whether or not the glass substrate 11 with a transparent conductive film to be imaged is located at a predetermined position. When the photoelectric switch 5a performs the detection, the photoelectric switch 5a transmits a notification signal N for notifying that the glass substrate 11 with a transparent conductive film is in a predetermined position to the image processing device 7a.

  The rollers 1A-1, 1A-2,... Are provided with a rotary encoder 6a, which detects the rotation speed and rotation angle of the rollers. The output of the rotary encoder 6a is transmitted as a pulse signal P to the image processing device 7a.

The image processing apparatus 7a includes a calculation unit that calculates the R, G, and B luminances separated by the color line sensor camera 2a to calculate the film thickness and haze ratio of the transparent conductive film.
A display device 8a and a printing device 9a are connected to the image processing device 7a so that an image processing result is output.

The transparent conductive film analyzer 10 having the above configuration measures the film thickness and haze ratio of the transparent conductive film, as will be described later. Thus, since the transparent conductive film analyzer 10 is provided on the production line, all the glass substrates 11 with a transparent conductive film are inspected.
Then, a photoelectric conversion layer is formed by forming an amorphous silicon thin film with a plasma CVD apparatus located on the downstream side, and a back electrode or the like is attached to manufacture a solar cell.

Next, the film thickness measurement and haze ratio measurement of the transparent conductive film performed by the transparent conductive film analyzer 10 having the above-described configuration will be described.
[Film thickness measurement]
The reflected light reflected from the glass substrate 11 with the transparent conductive film is imaged by the color line sensor camera 2a, so that it is spectrally divided into three primary colors R (red), G (green), and B (blue). Is done. Then, the luminance (intensity) of each of R, G, and B is taken into the image processing device 7a for each pixel in the imaging region.
Then, in the image processing apparatus 7a, the R, G, and B luminances are averaged over a range of 50 mm square, and then the following calculation is performed. The reason for averaging at 50 mm square is that the result with the least error is obtained, as will be described later with reference to the data of FIG.
In the image processing apparatus 7a, the film thickness of the transparent conductive film is calculated by calculating the respective luminances of R, G, and B according to the following equations.
Film thickness (μm) =
(The second largest value among the luminances of R, G, and B / the maximum value of the luminances of R, G, and B) × a + b
Here, a and b are constants and change depending on the composition of the transparent conductive film, the film thickness, the process, the type of the underlying film, etc., and the relationship between the film thickness and the luminance of R, G, B should be examined in advance. Determined by.
Also, the above arithmetic expression varies depending on the composition of the transparent conductive film and is determined by examining the relationship between the film thickness and the luminance of R, G, and B in advance. Specifically, the maximum value, the median value, and the minimum value are determined from the luminances of R, G, and B, and an arithmetic expression that best suits the actual film thickness is obtained by appropriately combining them.

Next, a specific example in which the film thickness of the transparent conductive film is actually calculated from the respective luminances of R, G, and B will be shown.
FIG. 3 is a plot of the brightness of R, G, and B for each sample.
It is shown that the brightness of R, G, and B is reversed for each sample. FIG. 4 shows the result of calculating the luminances of R, G, and B by the following equation.
Film thickness (μm) = second largest value of luminance of R, G, B / maximum value of luminance of R, G, B In other words, in the case of the above formula, in the above calculation formula, a = 1, b = 0.
In FIG. 4, the horizontal axis represents the number of samples, and the vertical axis represents the film thickness (μm). What is plotted based on the above arithmetic expression and what is actually measured for the film thickness are shown together.
From this figure, there is a very strong correlation between the result calculated from the luminances of R, G, and B and the film thickness. If two of the luminances of R, G, and B are used, the film thickness is It can be seen that it can be calculated.

[Haze ratio measurement]
In the case of haze ratio measurement, as in the case of film thickness measurement, the luminance (intensity) of each of R, G, and B is taken into the image processing device 7a for each pixel in the imaging region, and R, G, and B After each luminance is averaged over a range of 50 mm square, the following calculation is performed.
The calculation of the haze ratio measurement also differs depending on the type of the transparent conductive film and is determined by examining the relationship between the film thickness and the R, G, and B luminances in advance.
According to the inventor's knowledge, it is known that the best fit with the haze rate actually measured by the haze meter is obtained by using an arithmetic expression based on a linear combination of the luminance values of R, G, and B.

Next, a specific example in which the haze ratio of the glass substrate 11 with a transparent conductive film is actually calculated from the respective luminances of R, G, and B will be shown.
The haze ratio was calculated by the following equation using each luminance of R, G, and B.
Haze ratio = −0.086 × B + 0.13 × Y-21 × 100 / G−0.23 × G + 10 × 100 / B + 10 × 100 / R + 1.2 × (second largest among luminance of R, G, B) Value / maximum value of brightness of R, G, B) +25
Here, Y = 0.30 × R + 0.59 × G + 0.11 × B
FIG. 5 is a plot in which the calculated value by the above equation is plotted on the horizontal axis and the measured value measured with a haze meter is plotted on the vertical axis. In addition, the measurement of the haze rate by a haze meter was performed based on JIS K7361-1997.
As can be seen from this figure, each plotted point is almost close to a straight line of y = x. Therefore, the haze rate calculated based on the luminances of R, G, and B has a very strong correlation with the haze rate measured by the haze meter, and an arithmetic expression based on a linear combination of the luminances of R, G, and B is obtained. It can be seen that the haze ratio can be calculated if used.

FIG. 6 shows the haze ratio calculated after averaging an image obtained by the color line sensor camera 2a over a predetermined area.
FIG. 6A shows an average of 5 mm square, FIG. 6B shows an average of 10 mm square, and FIG. 6C shows an average of 50 mm square.
The multiple correlation coefficient in FIG. 6A is 0.9006, the multiple correlation coefficient in FIG. 6B is 0.9098, and the multiple correlation coefficient in FIG. 6C is 0.9338. From these, it can be seen that (c) averaged at 50 mm square has the largest multiple correlation coefficient, and if averaged at 50 mm square, the haze ratio closest to the measured value is calculated.

As described above, the transparent conductive film analyzer 10 according to the present embodiment has the following effects.
Since the transparent conductive film was irradiated with white light, the reflected light was split into three wavelengths of R, G, and B, and the film thickness of the transparent conductive film was calculated by calculating the luminance of these wavelengths. As long as the reflected light can be obtained, the film thickness can be calculated even if the interference of light is not obtained or the transparent conductive film having irregularities on the surface.

  Further, the transparent conductive film is irradiated with white light, the reflected light is split into three wavelengths of R, G, and B, and the haze ratio of the transparent conductive film is calculated by calculating the luminance of these wavelengths. Therefore, as long as the reflected light is obtained, the haze ratio of the transparent conductive film can be calculated without preparing a haze meter separately.

  Moreover, since only the reflected light can be obtained, the film thickness or haze ratio of the transparent conductive film can be calculated, so that it can be easily incorporated into the solar cell production line with a simple configuration. Therefore, 100% inspection of solar cells having a transparent conductive film is possible, and quality control is performed extremely well.

  In the present embodiment, the film thickness and the haze ratio are calculated using the three wavelengths of R, G, and B. However, the present invention is not particularly limited to the three wavelengths of R, G, and B. , R, G, and B may be used to calculate the film thickness and haze ratio using two wavelengths of light, or C (Cyan), M (Magenta), and Y (complementary colors). Four wavelengths of Yellow) and G (Green) may be used.

It is the perspective view which showed the transparent conductive film analyzer of this invention. It is the side view which showed the principal part of FIG. It is the figure which showed the brightness | luminance of R, G, B of reflected light for every sample. It is the figure which showed the film thickness of the transparent conductive film computed with the computing equation by this invention with the measured value. It is the figure which showed the haze rate of the transparent conductive film computed with the computing equation by this invention with the measured value. It is the figure which showed the haze rate computed after averaging each brightness | luminance of R, G, B for every predetermined area with a measured value.

Explanation of symbols

2a Color line sensor camera (spectral means)
3a Line illuminator (light irradiation means)
10 Transparent conductive film analyzer 11 Glass substrate with transparent conductive film

Claims (6)

  A transparent conductive film characterized in that the transparent conductive film is irradiated with light, the reflected light is dispersed into at least two wavelengths, and the film thickness of the transparent conductive film is calculated by calculating the light intensity of these wavelengths. Analysis method.   A transparent conductive film characterized in that the transparent conductive film is irradiated with light, the reflected light is dispersed into at least two wavelengths, and the haze ratio of the transparent conductive film is calculated by calculating the light intensity of these wavelengths. Analysis method. The light applied to the transparent conductive film is white light,
3. The transparent conductive film analysis method according to claim 1, wherein the reflected light is split into three colors of red, green and blue.   A transparent conductive film quality control method, wherein the quality of the transparent conductive film is managed using the transparent conductive film analysis method according to claim 1.   A solar cell comprising a glass substrate with a transparent conductive film quality-controlled by the transparent conductive film quality control method according to claim 4. A light irradiation means for irradiating the transparent conductive film with light;
A spectroscopic means for splitting the light reflected by the transparent conductive film into at least two wavelengths;
A computing means for computing the intensity of the dispersed light to calculate the film thickness and / or haze ratio of the transparent conductive film;
The transparent conductive film analyzer characterized by the above-mentioned.

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