JPS60196648A - Photometric apparatus - Google Patents

Abstract

PURPOSE:To make it possible to take out a photometric result at every arbitrary minute region on a specimen, by straightly moving a laser beam spot on the specimen and outputting a signal at a predetermined photometric position while integrating the same. CONSTITUTION:The laser beam from a beam source 1 is condensed to a specimen 4 and secondary beam transmitted therethrough is sent to a spectroscope 2. A specimen cell 3 is vibrated at a constant cycle by a vibration control unit 5 and the locus at the laser beam spot position on the specimen 4 forms a line. A photometric position determination means 12 generates a sampling trigger pulse (c) in synchronous relation to the control signal of the vibration control unit 5 and a sampling gate 14 passes a photocurrent signal (e) for a definite time. The photocurrent signal (e) passed through the sampling gate 14 at every sampling time receives the discrimination between a specimen signal (g) and a reference signal (f) by a discriminator circuit 15 and both signals are respectively sent to integrator circuits 16, 17 to receive integration and amplification.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention detects the physical properties, surface state, composition state, etc. of a sample by measuring the state of transmitted light, reflected light, phosphorescence, luminescence, etc. of the sample. This invention relates to a photometric device for use in photometry.

[Field of Application of the Invention] The present invention can be used, for example, to evaluate the uniformity and physical properties of synthetic resin films, etc.; This is useful when used for evaluation.

[Background of the Invention and Problems] Recently, with the aim of creating new technologies that go beyond conventional electronics, proposals have been made for molecular electronics and biochips in which individual molecules or a collection of a small number of molecules have the function of an electronic device. Amid these new trends, the single-molecule accumulation method is attracting attention as a technique for organizing highly ordered layered molecular assemblies. The monomolecular accumulation method is a method of creating ultra-thin films by stacking monomolecular films formed on water surfaces one by one on solid surfaces, and is a film system that allows for the design of components and structure.

In order to evaluate the absorption spectrum of the dye in such a cumulative film, a special photometric device is used because extremely minute changes in transmittance must be measured.

FIG. 1 is an explanatory diagram showing a conventional photometry device, in which a light beam is irradiated from a light source 1 to a sample 4 held in a sample cell 3 via a spectrometer 2, and a vibration control unit 5 is used to irradiate the sample 4 with light. The transmitted light is received by the photoelectron amplification unit 6 while being vibrated in a direction perpendicular to the beam, and the photocurrent based on this is integrated in the same phase as the vibration period of the sample. In addition, 7 is PS
D (phase sense detector), 8 is a recorder, and 9 is a wavelength setting device.

However, with the conventional photometry device described in 1-1, it is only possible to evaluate the average physical properties of the sample in the range in which the light beam spot is moved on the sample, and it is not possible to evaluate the average physical properties of the sample in the range in which the light beam spot is moved on the sample. There is a drawback that it is not possible to compare and evaluate the state of aggregation, etc. When measuring each minute area, especially in photometry for monomolecular films, it is meaningless unless you can measure extremely small changes, and if you simply amplify the signal for a minute area, it will be affected by noise. There is a problem in that even minute changes cannot be accurately measured. In addition, when trying to obtain evaluations for each microscopic area, it is said that the thinner the light beam is, the better; however, the light beam that passes through the spectroscope is spread by passing through a prism, etc., so it is difficult to converge it into a sufficiently narrow light beam. There are also problems.

On the other hand, for example, in Qi molecule-cumulative D, it is possible to design a structure such as a mixed monolayer consisting of multi-component components or a beta-accumulative layer in which monolayers of different compositions are combined and accumulated.
Evaluation of non-uniformity in a micro region within the plane of a fi thin film has become an important elemental technology in evaluating its physical properties. For example, in a mixed monomolecular film of a long-chain alkyl- or (-substituted merocyanine dye) and a long-chain alkyl carbon # (araxic acid, etc.), it is known that merocyanine merocyanines, timers, and J-aggregates exist. and
The film properties differ depending on the state of distribution of these. Therefore, what kind of distribution state these components have, and also lI,! How the distribution changes depending on pressure is an interesting problem in evaluating the physical properties of membranes. However, as mentioned above, research is currently hindered because conventional photometric devices cannot perform such evaluations.

[Object of the Invention] An object of the present invention is to make it possible to obtain photometry results for each arbitrary microregion on a sample, and to enable accurate comparative evaluation between the microregions.

[Summary of the Invention] The present invention makes it possible to make the light beam sufficiently narrow by irradiating the sample with the light beam without intervening a spectrometer, while also moving the light beam spot on the sample. This is a photometry device that is capable of determining the position before the photometry position, integrating the signals at this photometry position, and outputting the result as a photometry result.

[Structure and operation of the invention] The feature of the second structure of the present invention is that the light source of the light beam irradiated to the sample and the light beam spot of the sample 2 are moved so that the locus of the light beam spot forms a line. The present invention is a photometric apparatus having a moving means for moving the sample, a photometric means for spectrally measuring at least secondary light, and a photometric positioning means for determining a photometric position on a sample.

The light source in the present invention may be, for example, white light or the like, as long as it includes visible light, infrared rays, or ultraviolet rays, and the spectroscope may be the same as those commonly used. The photometric means means a means for deriving a desired I11 light result from the secondary light. The moving means may be any means as long as it can relatively shift the positional relationship between the light beam and the sample, such as one for moving the test sample 4, one for moving the light beam, or a combination of both. In the present invention, secondary light refers to transmitted light, reflected light, phosphorescence, or luminescence from a sample.

The allllll method converts the signal output based on the continuously received secondary light, which changes as the light beam spot moves on the sample, into a signal within an arbitrarily determined minute movement range of the light beam spot. It functions to separate and selectively take out. Therefore, in the present invention, by performing a search by moving the light beam spot in a linear manner on the sample #l and using this measurement positioning means, the measurement results for each arbitrary minute area on the search line are accumulated by the number of search cycles. This is obtained as follows. In addition, since the light beam is irradiated onto the sample without passing through a spectrometer, it can be made sufficiently narrow, and photometry results can be extracted for each extremely small area. By adjusting the positions of the light source side and the light receiving side, the device of the present invention can receive any secondary light such as transmitted light, reflected light, phosphorescence, or emitted light and generate 411 light.

[Embodiment] FIG. 2 is an explanatory diagram showing an embodiment of the present invention, in which a light beam emitted from a light source 1 is focused by a lens system 10 onto a sample cell 3 and a sample 4 held in the sample cell 3. The secondary light that has passed through it passes through the lens system 11 and the spectrometer 2.
sent to. The sample cell 3 is moved by a vibration control unit 1. The light beam spot 5 vibrates at a constant period, so that the locus of the light beam spot position on the sample 4- forms a line. The secondary light sent to the spectrometer 2 is spectrally separated and then sent to the photoelectron amplification unit 6, where the received optical signal is converted into a photocurrent signal. In addition, the test wood [4] is held in one half of the sample cell 3, and the light beam spot is spread from the sample 4-holding surface of the sample cell 3 to the non-sample-holding surface by the downward vibration of the sample cell 3. will be moved. Therefore, in order to obtain the photocurrent signal, there is a sample signal based on the secondary light transmitted through the holding surface of the sample 4, and a reference signal based on the secondary light transmitted through the non-held surface of the sample 4. is included.

The vibration period a of the sample cell 3 and the photocurrent signal due to the secondary light appearing in the same phase as this vibration are shown in Figures 3(a) and (b), respectively.
). (a) shows the vibration period a of the sample cell 3, (b) shows the photocurrent signal, and t in Fig. 3 is time;
■ is the voltage.

Conventionally, the two photocurrent signals are integrated over the entire area in the same phase, but in the present invention, a sampling trigger unit that generates the sampling trigger pulse C in synchronization with the control signal of the vibration control unit 5 is used. 12 is used as photometric positioning means. The timing of the generated sampling trigger pulse C is shown in FIG. 3(C). The sampling trigger pulse C is delayed by I (delay time) at an arbitrarily determined fixed time in the delay circuit 13 and then sent to the sampling time) 14. The sampling gate 14 is generated by this sampling trigger pulse C. Figure 3 (
The photocurrent signal from the photoelectron amplification unit 6 is opened for a certain period of time by the sampling pulse d shown in d), and only during that time, the photocurrent signal from the photoelectron amplification unit 6 is
) as a photocurrent signal e at the sampling gate 14
is passed through and amplified.

In this way, the photocurrent signal e passing through the sampling gate 14 every 2 sampling times is sent to the jt separate circuit 1.
After the sample signal g and the reference signal f are divided into the sample signal g and the reference signal f by 5r,
Each signal is sent to 4Jr circuits I6 and 17, where it is integrated and amplified. By the way, the photoelectric signal e is taken out for each specific minute region of the sample cell 3 or the sample 4, and is taken out multiple times due to the vibration of the sample cell 3, so the photoelectric signal e of the same minute region is It is possible to accumulate times. Finally, the signal is converted into a desired data signal I, such as transmittance or absorbance, by an arithmetic circuit in one day, and then outputted to the recorder 8 as a photometric result. Note that the output light of the photometry results may be output from a monitor television or the like instead of the recorder 8, and the photometry results can be displayed in various forms such as two-dimensional display or three-dimensional display. Further, the reference signal f is necessary to remove the influence of the presence of the sample cell 3 from the data signal (2), but it is not necessarily necessary depending on the type of photometry.

As mentioned above, the apparatus according to this embodiment has the following features: 1) The light beam is focused on the sample cell 3 and the sample 4, and the spectrum can be measured in a minute area; 2) The sample cell 3
3) By making the change in the position of the optical beam spot due to the vibration of the light beam correspond to the R delay time τ1 of the trigger pulse C, and by further changing the delay time τ1, it is possible to evaluate the spectra in different minute regions from the integrated signal. It is characterized by the fact that it is

Since the light beam is irradiated onto the sample 4 without passing through the spectrometer 2, the diameter of the light beam spot can be easily narrowed down to about lpm, which allows the microscopic area to be photometered and evaluated to be sufficiently small. can do. When the light beam spot is moved by vibrating the sample cell 3 as in this embodiment, it is preferable that the amplitude of the vibration be in the range of about 1 to 30 mm because the vibration can be easily turned off. Further, the sampling time of 2 is determined by the vibration period T of the sample cell 3 and the size of the light beam spot, but generally 2zT/100 is appropriate.

The moving means in this embodiment is a device configured to vibrate the sample cell 3, but it is also possible to use a device in which the sample cell 3 is fixed and the sample 4 is moved using some method using a light beam. It is possible. For example, it is possible to use a rotating mirror. The operating principle in this case is also exactly the same as in the embodiment. Such a change has many advantages when evaluating the physical properties of a thin film by applying an electric field, a magnetic field, etc. to the sample 4, and when measuring the sample temperature. Furthermore, although the movement trajectory of the light beam spot on the sample formed by the movement of the sample cell 3 or the light beam is linear (-dimensional), by using both together, a movement component orthogonal to the one-dimensional relative movement of one side is used. By giving the other side, the locus of the light beam spot can be easily made planar (two-dimensional). For example, if the vibration period of one is made sufficiently shorter than the other, the locus of the spot can cover the entire sample surface.

Furthermore, in this embodiment, the variables that can be changed independently are the wavelength or wave number of the spectrometer 2 and the delay time.
It must be possible to scan these two variables independently.

In this embodiment, the operation has been described on the basis of manually setting each delay time to 1. However, it is also possible to add a system that automatically scans 1 with a fixed spectral wavelength and a delay time. Furthermore, the present implementation also includes a multi-channel system in which the sampling gate 14 is opened in a time series arbitrarily determined from the sampling trigger pulse C, and the passed 9'i flow signal e is differentially amplified in accordance with the time series. This is possible as a variation of the example. This will be explained using the fIS4 diagram.

dl...dn in FIG. 4(a) are sampling pulses, and the sampling pulses are sequentially arranged in time series arbitrarily determined from the sampling trigger pulse C from dl to dn, and the AND circuit shown in FIG. 4(b) is used. G1”Gr
+ is supplied. And each sampling pulse d!
When ~dn is supplied, the photocurrent signal is sent to the ttSl~fJSn channel circuits through the AND circuits G and ~Gn, thereby outputting the photometry results for each minute area. In this case, the spectra of a large number of minute regions can be easily determined in one measurement, thereby speeding up the measurement. In such a system, digital amplification is better than analog amplification, and various modifications such as photon scouting and the use of computers are possible.

Furthermore, in this embodiment, by arranging the incident light and the spectrometer 2 on the rotating side with respect to the sample 4, it can be applied as a photometric device for measuring reflectance in a minute area.

[Effect of the Invention] As explained above, the effect of the present invention is to improve the spectral synergy in the micro region of a thin film, especially a monomolecular film or a monomolecular cumulative film, by improving the conventionally used photometric device. As well as being able to measure light in any minute area,
The advantage is that it is possible to evaluate spectral changes due to changes in relative position, ie, non-uniformity of dye distribution. especially,
Photometry results can be obtained by integrating signals from a specific minute area, and minute changes can be magnified by integration, so noise can cause inaccuracies, as would be the case when a single signal is amplified once in width. No worries.

Therefore, it is especially important to evaluate the uniformity and physical properties of thin films with high applicability, such as mixed monomolecular films and heterogeneous cumulative films, and to improve the uniformity of thin films.
1! There will be ripple effects such as improvements in materials and film-forming techniques that can be used to make J. Furthermore, since the light beam is irradiated onto the sample without passing through a spectroscope, the diameter of the light beam can be narrowed down, making it easy to make the minute area to be illuminated sufficiently small, and making it easier to improve the accuracy of the above evaluation.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a conventional photometric device, FIG. 2 is an explanatory diagram showing an embodiment of the photometric device according to the present invention, FIG. 3 is a timing diagram of each signal, and FIG. 4 is an explanatory diagram of a photometric positioning means. It is an explanatory view showing other examples. 1: Light source, 2 Spectroscope, 3: Sample cell, 4: Sample, 5:
Vibration control unit, 6: Photoelectronic amplification unit, 7: PSD, 8 recorders, 9: Wavelength setter, 10, +1: Lens system, 12: Sampling trigger unit, 13: Delay circuit, 14: Sampling gate. +5: Discriminator circuit, IG', +7: Integrating circuit, 18: Arithmetic circuit. Applicant Canon Co., Ltd. Agent Yutaka 1) Yoshio Figure 1 Figure 2 Figure 4

Claims (1)

[Claims] 1) A light source for a light beam that is irradiated onto a sample, a moving means for moving the light beam spot so that the locus of the light beam on the sample forms a line, and photometry that spectrally spectra and photometers at least secondary light. 1. A photometric device comprising: a photometric positioning device for determining a photometric position of a sample 1.