TWI313794B - - Google Patents

Description

1313794 ~~--- V. DESCRIPTION OF THE INVENTION (1) Field of the Invention: The present invention relates to an electronic component such as a semiconductor device board 4, a printed circuit liquid, and a developing waste liquid ^ = The photoresist is made of alkaline: = method, and concentration measurement - "inside, back-free technology: temple in semiconductor devices, 汸a hall + protruding parts, etc., electronic components such as printed circuit boards The ^ 或 玻璃 玻璃 玻璃 玻璃 玻璃 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Imaging with a developing solution and = for a developing solution:; dissolve:;; == is roughly divided into an exposure resist, and the main component of the manufacturing process of the m sub-component is a positive-type developing liquid. ,;;, the imaging liquid for photoresist is used in the case of an imaging solution. The negative-type photo-induced anti-synthesis agent also has any organic alkali which uses alkaline as an imaging liquid, as a ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, An alkaline developing solution such as a brush circuit board is added. If a carbon such as tetraalkylammonium hydroxide is used, the composition is such that: ϊ:::j is dissolved in the two gasification system by contact with air. Hydroxyl ions of the alkaline component of the counter ion are consumed, for example, ions form bicarbonate or carbonate (as described in 2042-5562-PF(Nl).ptd, page 6 1313794 V. Description of invention (2), also known as The liquid is supplied to the class for the dissolution of the state of the cationic compound, and is dissolved, and in recent years, it is determined by the precise processing steps and is effective for semi-conducting if an alkaline image effect is used. 0 2% by weight Normally, the liquid and the reconstituted components are measured by a differential titration device. Specially measured, the invention is subject to the invention: However, the carbonated salt is a balanced ion, and has a photoactive activity. Carbonation-based salts, carbonate-based salts due to the presence of an opt-in imaging solution in the semiconductor process, and LSI and LCD requirements for photo-sensitivity and productivity. The imaging component is 2. 3 8 The right range is used in the developmental imaging solution for the concentration modulation step, the conductivity meter, the super conductivity meter and the ultra-wide use. The experimental imaging component system, the ion and the detection It is in a state of being free in the liquid (hydrogen oxidizing property. Therefore, the activity of the developing image is reduced by the carbon dioxide-based. In the case of alkaline imaging, a small amount of carbonic acid salt is used repeatedly, and the concentration of carbon dioxide gradually increases. Trends: Fineness and high integration are progressing. From the point of view, the fine pattern is steadily raised for correct control of the concentration of the developing liquid. The developing solution used for the process is known to have a concentration of The most effective and quantitative dilution of the soil adjusted to this concentration is used. In the case of an imaging solution such as a TA Η titration device or a potential sonic concentration meter, a sound wave concentration meter such as a TA Η titration device or a potential sonic concentration meter is used as a continuous component. The subject of the decision: Even if a high-performance concentration measuring device is used, it is alkaline

2042-5562-PF(Nl).ptd Page 7 1313794 V. DESCRIPTION OF THE INVENTION (3) The concentration control of the image liquid, that is, the equivalent conductivity to measure the total management conductivity is compared with the target alkaline imaging liquid. By means of the (hydroxide) fruit, the concentration of the derivative is used to show that the imaging of the image of the target liquid contains alkaline imaging. To solve the problem, you should try it out. As a result, there is a problem of the acid salt. However, it is possible to produce a concentration of a carbonaceous component or a supersonic. From the cumbersome concentration, the electric potential controls the image to the concentration of the invention, and the concentration component of the liquid has an acid salt concentration. The fundamental concentration meter has a supply titration technique based on the concentration step. difficult. Alkaline imaging solution 'by titration at this concentration 'corrected for concentration' then corrects the conductivity of the imaging component at the lower j-degree of the hydroxide concentration in the imaging step to determine the free imaging component The result of the knot 'has been controlled with higher hydrogen oxygen to contain alkaline imaging to provide a correct and effective display. Another object of the present invention is to provide a means for measuring the degree of concentration, management, or regeneration of a chemical image. The difficulty of controlling the concentration of an alkaline imaging solution is determined by the concentration of the test imaging liquid. In the past, for carbon, within the allowable range, it is considered that the technology used in this time was not measured, and it was unexpectedly found that the correct imaging components of these carbons have the correct activity. point. / The reason for the difficulty in controlling the concentration of alkaline imaging liquid is

1313794 V. INSTRUCTIONS (4) After the alkaline imaging/liquid is obtained, a part of the alkaline imaging component has become a carbonate salt; and the point of increase of the carbonate salt in the process of use; The concentration of all the developing component containing these carbonate-based salts was measured as a point of effective imaging component concentration. Therefore, various steps such as a concentration adjustment step of the developing solution supplied to the developing step, a recovery step (including a concentration step), a regeneration step (dilution step), and the like are performed for measuring the free display of hydroxide or the like in the developing solution. As a result of investigations on the concentration of the components and the techniques, it has been found that by measuring the concentration of all the imaging components in the various test solutions and simultaneously measuring the concentration of the carbonic acid salts, the influence of the carbonic acid salts can be eliminated, and the freeness can be accurately measured. Imaging component concentration. Based on this, it has been found that the above problems can be solved and the present invention has been completed. That is, the present invention provides the following methods. (1) A method for measuring the concentration of a developing solution containing an alkaline developing component, and having a step of measuring the concentration of a free alkaline developing component in the developing solution. (2) A method for measuring a concentration of a developing solution containing an alkaline developing component, comprising the steps of measuring the concentration of all the alkali imaging components in the developing solution, and measuring the carbonic acid salts in the developing solution The method of the concentration step. (3) The method according to (2), wherein the neutralization titration device, the potential difference titration device, the conductivity measuring device, the phase difference measuring device, and the ultrasonic propagation velocity measuring device are used to measure the foregoing All alkaline imaging component concentrations.

2042-5562-PF(Nl).ptd Page 9 1313794 )2 (5C system such as Ming 3, 4, /IV 5 or carbonized oxygen, the use of the law

The fixture is set to measure carbon dioxide. Pre-existing concentrated salt, the sulphuric acid carbon is described in the previous test. (4 Packing as set 5) Measuring C line outside the red containing package to test carbonized oxygen, such as the practice The method of sputum method for the liquid image of the same system, Γ方丨1 (疋 肩 则 则 则 则 d d h h h h h h h h h h h h h U U U U U U U U U U U U U U U U Showing 35 items 0 to 1-7, 7), 7), {Steps of the step 1 of the item 1 in the line of the item ・ The IL type contains the liquid waste of the method and has a sudden step The method of determining the liquidity of the 方 定 所有 所有 所有 所有 所有 所有 所有 M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M Imaging of the image shows that the sex C base is contained in the lower part. A basic method is used to make 10, degree {methods, imaging, explicit effect, some of the required carbon formation, degree I, concentration, 〇 image method, alkalinity, tube, fullness, concentration, concentration, concentration The liquid-distributed imaging image shows that the opposite is alkaline

Set the measurement 1) degree C 嚷 the first liquid image is marked into a strong image, the appearance is like a base, and the alkali salt is one of the alkali-like salts. The system is acid C, and is placed in a package. The concentration of the rich image into the image of the concentrated image of the alkali image is determined by the imaging solution in the carbon solution of the central acid liquid full acid image. The salt of the degree, the measured or installed, the refilled liquid, the waste concentrated image, the apparent appearance of the image, the alkali-like sulphate, the liquid-containing species, a system, }测2 has (with

2042-5562-PF(Nl).ptd Page 10 1313794 V. INSTRUCTIONS (6) ----___ Carbonated salts in the imaging solution for the concentration of all alkaline imaging components in the imaging solution The concentration of the device. According to these inventions, by measuring the concentration of the imaging component in the free developing portion and the concentration of the carbonic acid salt, it is possible to include a developing component capable of exhibiting imaging activity. ^, 疋 concentration adjusts the alkalinity of the correct control concentration in the image step. Therefore, it is necessary to implement a correct and effective imaging step. fly. According to these results, according to these inventions, it is possible to detect 3 by measuring the free intensity, or the concentration of all the imaging components, the carbonic acid salt type inversion 71 // 汊 汊 汊, The imaging activity of the imaging solution of the diagnostic imaging component. Embodiments Hereinafter, embodiments of the present invention will be described in detail. The concentration measuring technique for the developing solution containing the alkaline developing component of the present invention is to measure the concentration of the free alkaline developing component in the developing solution or to measure the concentration of all the alkaline developing components in the developing solution and The concentration of acid salts in the developing solution. Further, by using the concentration measuring technique, that is, the concentration measuring method and the concentration measuring device', it is possible to achieve concentration adjustment (dilution) of the developing solution or preparation or recovery or regeneration of the developing waste liquid.

(Experimental imaging component) The organic imaging test used in the production of various electronic components and the like is not particularly limited, but is preferably a tetraalkylammonium hydroxide (TAA®). . Examples of T A A Η include tetradecyl hydroxide (ΤΜΑΗ), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrahydric hydroxide.

2042-5562-PF(Nl).ptd

1313794

An alkaline imaging component contained in the substance. The so-called all alkaline imaging component means

In the developing solution, it can be paired with a hydroxyl ion and other anions, and a component having a developing activity in a free state. Specifically, all of the atopic imaging components are composed of a free basic imaging component and an inspective imaging component (typically a carbonate-based salt) paired with an anion other than a hydroxyl ion. The amount of all alkaline imaging components is the sum of these basic imaging components. In particular, the concentration adjustment step such as the step of diluting the developing solution to prepare a developing solution of a predetermined wave degree, and the dilution before the use of the developing waste liquid is regenerated.

2〇42-5562-PF(Nl).ptd Page 12 1313794 V. Description of the invention (8) Surface, except for the amount of hydroxylate bicarbonate ion, which can be used as the total of free imaging components (free direct determination of free test) The concentration of the carbonic acid salt component can be measured and the conductivity can be measured at various concentrations. The pH is used for the smashing process. (In the past, all the neutralization and titration can be used for titration of all alkaline carbonation ions. However, the same solution has a tendency to be inferior to the test imaging. Therefore, it is possible to classify the carbonic acid-based imaging and the alkaline imaging into a free test image. The concentration is measured by, for example, a ρ Η meter and a phase difference device as a test method. The titration and the alkaline portion of the electric portion are simultaneously obtained to obtain a developing component; and only the free quantification is performed. The continuous development of the sexual imaging component, in this method, The composition is combined with the rigorous measurement of the invention in order to have the main ion. The composition, the obtained. (Neutralization concentration is determined. The point of the system, the difference of the drop component. That is, the addition of the test and the swim can also be in the air, the free is not more south of the negative ion carbonate ion and thus, all alkaline The developing component and the alkaline component constituting the carbonic acid salt are each drip, and the chlorination imaging concentration is determined by measuring the total alkali concentration, and all the devices, electricity, and super The sonic concentration method, the titration device at the point of accuracy is difficult to alkaline. It is preferred that the imaging is an alkaline imaging, such as a differential titration meter. For example, the components are neutralized by a general neutralization titration, and the acid is formed by deacidification to form a carbon component, and the titration system of the salt-developing imaging component is separately titrated. The carbon dioxide concentration in the titration operation is more negligible than the actual. Quantitative accuracy, all testability

2042-5562-PF(Nl).ptd Page 13 1313794 V. DESCRIPTION OF THE INVENTION (9) The imaging component is mostly affected by carbon (or the problem of a carbonated component of a carbonated component of a vaporized carbon. The equivalent point U of the acid salt, such as a non-agent, is determined by a conductivity meter, a rate meter, and a phase difference between the free carbonic acid salts measured by other means. The measurement data is determined by the titration method of the carbonic acid salt based on the image component or the liberation rate, the sensitivity of the carbonic acid salt, and the like, by being free from the oxidation in the air: Affected by the installation of f' or in the state of being unaffected by air = (or not easily affected), to obtain: VIII, obtained by subtracting the otherwise obtained = degree from all alkaline imaging components The free basic component is solved by this. First, although the pH and potential are determined for the determination of the end point of the titration, the present invention preferably uses a method of determining the end point of arrival by potentiometric titration. It is also possible to make a t-sonic densitometer and a phase difference densitometer from the viewpoint of continuous measurement on the pipeline. When a measuring device such as a conductive concentration meter or an ultrasonic concentration meter is used, correction of a standard solution of a concentration detecting device such as a base concentration titration or potentiometric titration, and a standard solution based on an alkaline developing component are used. Correction, this kind of school is implemented. With this correction, the relationship between the data based on the conductivity meter or the supersonic measurement and the respective concentrations can be determined at least within the concentration range of the full range to be controlled, and then all the qualitative imaging components can be applied. The degree of (the sum of the test imaging components of the free diagnostic imaging component). The present inventors have found that, for example, the conductivity of all of the basic alkaline imaging component concentrations of 2.38% by weight has a free basic imaging component and a conductivity + sensitivity. In other words, it can be seen that the free- and eight-degree carbonic acid salt alkaline imaging components of the wave eight are included.

2042-5562-PF(N1).ptd Page 14 1313794 V. Description of the invention (ίο), the conductivity is proportional to the concentration A and the concentration of 0.5 B. On the other hand, the concentration of carbonic acid salts, as described above, is affected by (or is not susceptible to) the influence of carbon dioxide in the air, or is not affected by carbon dioxide in the air (or is not easily affected). It is preferable to measure it in the state. As a device which is not affected (or is not easily affected) by carbon dioxide in the air, a method of directly measuring the amount of inorganic carbon or the amount of carbon dioxide in the developing solution can be mentioned. In general, since the measurement time of these devices is short or the measurement environment is limited, the amount of carbon dioxide in the developing liquid at the time of measurement can be accurately measured. As a measuring device for inorganic carbon or carbon dioxide, various conventional devices can be used, but in particular, a commercially available carbon dioxide sensor (non-dispersive infrared carbon dioxide concentration meter) or the like is preferably used. The sensor has means for adding acid to the test liquid to generate C 02, and means for detecting co2 produced by infrared light. The co2 generating device includes a gas generating tank that stores an inorganic strong acid solution such as phosphoric acid, a device that supplies the test liquid to the tank, a device that introduces a carrier gas such as an inert gas such as argon or air into the tank, and a tank. The clean space gas is delivered to the device of the infrared detecting device. In the co2 generator, when the test liquid is introduced into the tank, in the inorganic strong acid solution, the carbonic acid salts are transported into the clearance space of the tank by the formation of molecular co2 by ions. The carrier gas is then transported to the infrared line detection device via the transport device. In the infrared detecting device, infrared rays corresponding to the characteristic absorption wave number range of co2 were irradiated, and the C 02 concentration was measured from the absorption intensity. Since the concentration of inorganic carbonic acid or co2 in the developing solution is considered to be derived from inorganic carbonates, the carbon of the alkaline developing component can be determined from these concentrations.

2042-5562-PF(Nl).ptd Page 15 1313794 V. DESCRIPTION OF THE INVENTION (11) When the concentration of the acid salt is determined, the free base can be obtained from all the tests. The free basicity of the phase difference concentration is apparent to the concentration of the imaging component of all the alkali-developed carbonic acid salts. By having this, it is possible to provide a pipeline with a positive disc. Therefore, it is possible to further reduce the liquid crystal by the concentration step of the step of performing the imaging waste, and the concentration of the most active alkaline image. because. In the first table, the concentration of the alkaline developing component and the concentration of the concentrated component of the carbon-free basic developing component are subtracted from the concentration of the carbonic acid developing component. Further, the concentration between the concentration of the image component such as the ultrasonic concentration meter and the measurement data of the carbonic acid salt component and the measured value can be the concentration of the acid salt. As described above, by the concentration of the salt, it is easy to obtain the concentration by using the conductivity form, and in the concentration and the equivalent system obtained in advance, the concentration of the free alkaline bismuth concentration can be easily obtained from the concentration. The step of diluting the step after the liquid is transported (the recovery of the established ampoule under the seeding step, and the step of measuring the step-by-step process in the step of determining the step of the semiconductor, the step of performing the rich image activity from the alkaline, effective enough The substrate can be correctly imaged in the accuracy or concentration recovery step of the concentration measurement liquid or the concentration recovery step, and the photometric liquid concentration step is performed to perform the imaging measurement device and the concentrated display. The measurement is concentrated on the development of the liquid, and the first step of the liquid supply step. Set, display step, and then have visibility. Based on the steps, you can also wait for the steps and so on. And bad to be based on the corresponding alkaline imaging fluid (TMAH) in the air

2042-5562-PF(Nl).ptd Page 16 1313794 V. INSTRUCTIONS (12) The results of the internal reaction time and the titration method to determine the concentration of all alkaline components and carbonates, and the determination based on carbon dioxide (Infrared carbon dioxide detecting device, hereinafter referred to as this method.) The results of the acidity wave are compared, and the results are as follows. [Table 1] No

As shown in the first table, the y, the points are still fixed. (5) Relative: make / over-station time 'all alkaline imaging, based on neutralization titration half from = the carbonation concentration of this method produces a large initial change (station time 〇 /, sulphate concentration change but no So large, but at a larger value (the difference is 1. 1 〇 曰 曰. Compared with the results of this method, the result shows that the fruit is slightly older than this method, even after 30 minutes, the knot is generally considered to be neutral. Drop: the difference is 0 · 0 0 5 wt%). If this is the case, therefore, according to this summary: in the ten test time, c 〇2 dissolved in the sample solution to produce carbon dioxide produced by the 42 fruit can prove, In the measurement operation, the phenomenon of titrating the carbonate by the effect of the absorption of the invention. According to the present invention, the concentration of the developing solution at the target, θ is sufficient to properly control the step of containing the alkaline developing component. The concentration and development of the imaging solution can be used to achieve a correct and effective imaging technique, which can provide a measurement technique, and based on the concentration management of the concentration imaging solution

2042-5562-PF(Nl).ptd

Page 17 1313794 V. INSTRUCTIONS (13) Technology for the recovery or regeneration of waste liquids. Further, by using such a management method, it is possible to improve the yield and quality of the light treatment step in liquid crystal or semiconductor manufacturing.

2042-5562-PF(Nl).ptd Page 18 1313794 Simple illustration of the diagram 2042-5562-PF(Nl).ptd Page 19

Claims (1)

Annual sand 1 βθ oblique 3 ' ____1 case number 92106924 year f month date revision year _ VI. Patent application scope 1. A method for determining the concentration of a developing solution containing an alkaline imaging component, including: measuring all of the imaging liquid a step of determining the concentration of the alkaline developing component; and a step of measuring the concentration of the carbonic acid salt in the developing solution, wherein the concentration of the carbonic acid salt is subtracted from the concentration of the entire alkaline developing component to obtain a free base The concentration of the sexual imaging component. 2. The method according to claim 1, wherein the step of measuring the concentration of all of the alkaline imaging components is performed by a neutralization titration device, a potentiometric titration device, a conductivity measuring device, a phase difference measuring device, and a super The selected device among the groups formed by the sound wave propagation velocity measuring device. 3. The method of claim 1 or 2, wherein the concentration of the carbonic acid salt is determined by an infrared carbon dioxide detection method. A method of preparing a developing solution, comprising the step of carrying out a method for measuring a concentration of a developing liquid as described in claim 1 or 2. A method for recovering a developing waste liquid, comprising the step of carrying out a method for measuring a concentration of a developing liquid as described in claim 1 or 2. A method for regenerating a developing waste liquid, comprising the step of carrying out a method for measuring a concentration of a developing liquid as described in claim 1 or 2. A method for managing a concentration of a developing solution containing an alkaline developing component, comprising the step of measuring a concentration of a developing solution as described in claim 1 of the patent application. 2042-5562-PFl(Nl).ptc Page 20