CN219010090U

CN219010090U - System for preparing nano integrated circuit cleaning water

Info

Publication number: CN219010090U
Application number: CN202223076331.2U
Authority: CN
Inventors: 郑伟; 杨光明; 程星华; 李功洲; 王立; 陈保红
Original assignee: China Electronics Engineering Design Institute Co Ltd
Current assignee: China Electronics Engineering Design Institute Co Ltd
Priority date: 2022-11-16
Filing date: 2022-11-18
Publication date: 2023-05-12
Anticipated expiration: 2032-11-18

Abstract

The utility model discloses a nano-meterThe preparation system of the nano integrated circuit cleaning water comprises a pre-desalting system, a primary pure water system, a deep desalting system and a polishing system, wherein the pre-desalting system comprises a urea oxidative decomposer, an active carbon absorption tower and a composite ion exchange tower, the primary pure water system comprises a reverse osmosis device, the deep desalting system comprises a mixed ion exchange tower, a first mixed photolysis absorber and a first vacuum membrane degassing device, and the polishing system comprises a catalytic mixed photolysis absorber, a second vacuum membrane degassing device and an ultra-filter; not only can improve the degradation efficiency of the ultra-low molecular organic matters in the cleaning water, but also can lead the dissociation constant to be less than 10 ^‑9 The weakly ionized impurities in (2) are reduced to below 1ng/l, and the concentration of the weakly ionized impurities can be controlled within 1 mug/l at the POD end by effectively quenching the photolytic secondary oxidant.

Description

System for preparing nano integrated circuit cleaning water

Technical Field

The utility model relates to the technical field of ultra-pure water preparation of integrated circuits in nano processes, in particular to a system for preparing nano integrated circuit cleaning water.

Background

The cleaning water is used for integrated circuit fabrication and is used as a cleaning rinse in wet, photolithography, and like fabrication steps. In a typical cleaning water preparation system, various pollutants (such as metals, ions, particulate matters, organic impurities, bacteria and dissolved gases) in water are removed by using mechanical filtration, membrane filtration, deionized, ultraviolet oxidation, degassing and other technical means, and the prepared high-purity ultrapure water is subjected to POD end detection and is supplied to various manufacturing processes for cleaning or dosing.

Total Organic Carbon (TOC), microparticles, metal compounds, and boric acid and dissolved silicon with very low ionization constants can be used as conventional standards for evaluating the quality of the washing water, and some low molecular weight compounds such as isopropyl alcohol (IPA), methanol (CH 4O), and urea (CH 4N 2O) are also found in the POD end detection. Because of the challenges of removing hydrophilic and non-surface-charged low molecular organics (e.g., methanol) by RO, these ultra-low molecular organics penetrate a large proportion of single or dual stage RO membranes that have otherwise high interception efficiency at neutral pH, making it extremely difficult to achieve final production requirements for TOC <1ppb at the POD end.

On the process side (POE), as the feature size of semiconductor devices is scaled down, oxide layers, such as native oxide, gate oxide, and tunnel oxide, are all affected by ultra-low molecular organic compounds in the cleaning water. The organic compound containing polar (-OH) groups forms strong bonds with oxygen of the oxide layer and will also cause oxide breakdown and voltage leakage.

Research shows that certain low molecular organic matters such as methanol can be effectively degraded by vacuum ultraviolet rays, but the problem of how to remove the strong oxidizing products and the excessive oxidant in the photolysis process in the subsequent process is new. Along with the remarkable effect of AOPs technology application, free radical composite oxidants commonly appear in a nano-scale integrated circuit ultrapure water preparation system, and the secondary oxidants have strong oxidation potential and have degradation effect on materials such as resin in the cleaning water preparation process.

The metal ions are closely related to the yield of semiconductor components, and ion contamination can cause poor crystallization of chips and degradation of the insulation and voltage resistance of a gate oxide layer, thereby causing electric leakage and breakdown and changing the resistivity of a substrate.

The presence of fine particles in the cleaning water may cause open or short circuits in oxidation, diffusion, deposition, metallization, etc., and particularly particles of 100nm or more may easily cause defects in lithography, generate pinholes, and deteriorate the adhesion performance of the photoresist. In addition, the falling of the welding oxide of alloy steel materials such as stainless steel in the preparation system is also a risk source for causing the breakage of the hollow fiber membrane at the tail end and even the ultra-standard microparticles.

Therefore, in the preparation of the cleaning water, not only small molecular organic matters, boric acid which is a weak ionized impurity and dissolved silicon are deeply removed, but also corrosive matters and metal particles are prevented from falling off or being released into the treated water, and especially in the refining treatment section, design choices and creative thinking about metal minimization or demetallization are made on the materials of vessel shells such as a reactor, an exchange tower and the like and overcurrent parts such as pipelines, valves, sampling tanks and the like.

The above information disclosed in the background section is only for enhancement of understanding of the background of the utility model and therefore may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The utility model aims to provide a system for preparing nano integrated circuit cleaning water, which is suitable for preparing nano IC manufacture, is especially suitable for preparing and integrating ultrapure water for advanced process (with the characteristic dimension of 0.028 μm or below) cleaning of high-end chip production, and effectively solves the technical problems of deep degradation and removal of ultra-low molecular organic matters, microparticles and weakly ionized inorganic salts, demetallization of overcurrent materials, quenching of trace photolysis secondary oxidant and other industry focus.

In order to achieve the above object, the present utility model provides the following technical solutions:

the preparation system of the nano integrated circuit cleaning water of the utility model comprises:

the pre-desalting system performs pre-desalting on raw water to obtain shallow desalted water, and comprises a urea oxidation decomposer using an advanced oxidation technology, an active carbon absorption tower for absorbing residual oxidant and a compound ion exchange tower for pre-desalting, which are sequentially connected in the water flow direction;

the primary pure water system is connected with the pre-desalting system and performs membrane method desalting on the shallow desalted water to obtain primary pure water, and the primary pure water system comprises a reverse osmosis device;

The deep desalting system is connected with the primary pure water system and is used for deep desalting the primary pure water to obtain secondary pure water, and the deep desalting system comprises a mixed ion exchange tower for removing soluble salt, a first mixed photolysis absorber for removing organic carbon and weakly ionized impurities and a first vacuum membrane degassing device which are sequentially connected in the water flow direction;

the polishing system is connected with the deep desalting system and polishes the secondary pure water to obtain nano-process integrated circuit cleaning water, and comprises a catalytic mixed photolysis absorber for polishing, a second vacuum membrane degassing device for removing dissolved gas and an ultra-filter for removing microparticles, which are sequentially connected in the water flow direction.

In the technical scheme, the preparation system of the nano integrated circuit cleaning water provided by the utility model has the following beneficial effects: compared with the prior art, the utility model is a multifunctional continuous flow preparation system, which is organically coupled with a pre-desalting system, a primary pure water system, a secondary pure water system and a polishing system, and can respectively remove trace metal ions, weakly ionized impurities and low molecular organic matters to extremely high limiting values of ppq grade (gigabit), ppt grade (trillion) and ppb grade (billion), and control the free radical composite oxidant to be in the sub ppb grade. Not only solves the problem that the trace removal of the ultra-low molecular organic matters (carbonamide) in the cleaning water is difficult <1. Mu.g/l), with dissociation constant less than 10 ^-9 The weakly ionized impurities (such as boron) are reduced to below 1ng/l, and the concentration of the weakly ionized impurities (such as boron) at the POD end is controlled within 1 mug/l. The excellent effect meets the ultra-pure water preparation requirement of the nano-process integrated circuit with the characteristic size smaller than 3 nm. In addition, the integrated treatment device which reduces the equipment quantity, saves the space requirement, has compact structure and is more beneficial to pollution protection obviously optimizes and innovates the design for the process layout of the power station and the polishing area of the prior process IC factory.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present utility model, and other drawings may be obtained according to these drawings for a person having ordinary skill in the art.

Fig. 1 is a schematic structural diagram of a system for preparing nano integrated circuit cleaning water according to an embodiment of the present utility model.

Fig. 2 is a schematic cross-sectional structure of a first hybrid photolytic absorber U-PSA of a nano integrated circuit cleaning water preparation system according to an embodiment of the present utility model.

Fig. 3 is a schematic cross-sectional structure of a catalytic hybrid photolytic absorber U-PMB of a nano integrated circuit cleaning water preparation system according to an embodiment of the present utility model.

Fig. 4 is a schematic A-A cross-sectional structure of a catalytic hybrid photolysis absorber U-PMB of a nano integrated circuit cleaning water preparation system according to an embodiment of the present utility model.

Fig. 5 is an enlarged schematic diagram of a circle of a catalytic hybrid photolysis absorber U-PMB of a system for preparing nano integrated circuit cleaning water according to an embodiment of the present utility model.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present utility model more apparent, the technical solutions of the embodiments of the present utility model will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present utility model, and it is apparent that the described embodiments are some embodiments of the present utility model, but not all embodiments. All other embodiments, based on the embodiments of the utility model, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the utility model.

Thus, the following detailed description of the embodiments of the utility model, as presented in the figures, is not intended to limit the scope of the utility model, as claimed, but is merely representative of selected embodiments of the utility model. All other embodiments, based on the embodiments of the utility model, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the utility model.

In order to make the technical scheme of the present utility model better understood by those skilled in the art, the present utility model will be further described in detail with reference to the accompanying drawings.

As shown in fig. 1, the system for preparing nano-integrated circuit cleaning water includes,

the pre-desalting system is used for pre-desalting raw water to obtain shallow desalted water, and comprises a urea oxidative decomposer 300, an active carbon absorption tower 301 and a compound ion exchange tower 302, wherein the urea oxidative decomposer 300 is used for degrading carbonamide low-molecular organic matters, the active carbon absorption tower 301 is used for absorbing residual oxidants and hydrophobic organic matters with molecular weight of 500-3000 Da, and the compound ion exchange tower 302 is used for pre-desalting, and the compound ion exchange tower comprises a cation exchange tower and an anion exchange tower;

the primary pure water system is connected with the pre-desalting system and performs membrane method desalting on the shallow desalted water to obtain primary pure water, and the primary pure water system comprises a reverse osmosis device 303;

a deep desalination system which is connected with the primary pure water system and carries out deep desalination on the primary pure water to obtain secondary pure water, wherein the deep desalination system comprises a mixed ion exchange tower 304 for removing soluble salt, a first mixed photolysis absorber 305 for removing organic carbon and weakly ionized impurities and a first vacuum membrane degassing device 318 which are sequentially connected in the water flow direction;

The polishing system is connected with the deep desalting system and polishes the secondary pure water to obtain nano-process integrated circuit cleaning water, and comprises a catalytic mixed photolysis absorber 306 for polishing, a second vacuum membrane degassing device 307 for removing dissolved gas and an ultra-filter 308 for removing microparticles, which are sequentially connected in the water flow direction.

The pre-desalting system further comprises a production water tank, a first heat exchanger 310, a multi-medium filter 311, a filtering water tank 312 and a pre-desalting water tank 313 which are sequentially connected in the water flow direction, wherein the urea oxidative decomposer 300 is connected to the rear end of the filtering water tank 312, and the composite ion exchange tower 302 is connected to the front end of the pre-desalting water tank 313.

The primary water purification system further includes a cartridge filter 314 and an RO water tank 315, and the reverse osmosis unit 303 is disposed between the cartridge filter 314 and the RO water tank 315 in the water flow direction.

The deep desalting system comprises a mixed ion exchange tower 304, a first fine filter 316 and a first vacuum membrane degasser 318 which are sequentially connected in the water flow direction, and the first mixed photolysis absorber 305 is arranged between the mixed ion exchange tower 304 and the first fine filter 316.

The polishing system comprises a pure water storage tank 320, a second heat exchanger 321, a second fine filter 322, a second vacuum membrane degasser 307 and a terminal ultra-filter 308 which are sequentially connected in the water flow direction, and a catalytic type mixed photolysis absorber 306 is arranged between the second heat exchanger 321 and the second fine filter 322.

The radiation source of the urea oxidation decomposer 300 is a UV or VUV mercury vapor or low pressure high intensity amalgam arc discharge source.

The first hybrid photolytic absorber 305 or the catalytic hybrid photolytic absorber 306 includes:

at least one first housing which is a transparent, thermally insulating hollow enclosure;

at least one radiation light source arranged in the hollow closed structure to form a vacuum radiation cavity;

a second housing surrounding the at least one first housing;

the connecting cover is arranged at the top of the second shell;

the lower support pore plate is arranged at the bottom of the second shell, the lower support pore plate, the second shell inner wall, the first shell outer wall and the connecting cover form a first reaction cavity, the first reaction cavity forms a photolysis zone under the irradiation of the vacuum radiation cavity, water to be purified enters the first reaction cavity from the lower support pore plate and flows out of the upper part of the second shell to form a water flow channel, and the water flow channel is at least partially overlapped with the photolysis zone to photocatalytically oxidize the water to be purified to form first treated water;

a third housing having a bottom wall below the lower support orifice plate and a side wall extending upwardly from the bottom wall, the side wall circumscribing an opening, the side wall surrounding the second housing;

A top cover detachably covering the opening;

the first pore plate, the side wall, the outer wall of the second shell and the top cover form a sealing cavity, and the first treatment water enters the sealing cavity from the first reaction cavity;

one end of the second pore plate is fixed on the side wall, the other end of the second pore plate is fixed on the outer wall of the second shell, and the second pore plate, the side wall, the outer wall of the second shell and the bottom wall form a water collecting cavity;

and the second reaction cavity is formed by the first pore plate, the side wall, the outer wall of the second shell and the second pore plate.

The inlet penetrates through the bottom wall and is communicated with the first reaction cavity;

and the outflow port penetrates through the side wall and is communicated with the water collecting cavity.

The second pore plate is provided with at least one tower-shaped water distributor.

The first shell, the second shell and the third shell are of a central symmetrical structure with a central axis.

The raw water is not limited to one of a plurality of water bodies such as municipal tap water, recycled water or in-plant recycled water. After being subjected to turbidity removal and temperature rising through the multi-medium filter and the first heat exchanger, the wastewater enters an advanced oxidation system Oxi-RU+GAC from a filtering water tank.

The urea oxidative decomposer Oxi-RU adopts photocatalysis hydrogen peroxide or a plurality of oxidants, and utilizes oxidative free radicals to degrade amide low molecular organic matters, such as carbamide (urea), acetamide and the like. The urea oxidative decomposer Oxi-RU is arranged at the rear end of a filtering pool of a pretreatment section, aims at removing carbonamide (CH 4N 2O) and Trihalomethane (THMs) substances in tap water or reclaimed water, and is used for cleaning formulation, steam drying and isopropyl of photoresist dilution in a semiconductor manufacturing processHigh purity wet chemical residues such as alcohol (IPA), ethanol (C2H 6O), acetone (C3H 6O), and methyl ethyl ketone (CH 3COCH2CH 3). The urea oxidation decomposer Oxi-RU may cooperatively employ a novel coupling of multiple oxidants, such as VUV/H ₂ O ₂ +S ₂ O ₈ ^2- 、VUV/H ₂ O ₂ +HSO ₅ ^- Or VUV/H ₂ O ₂ +(NH ₄ ) ₂ S ₂ O ₈ Etc., wherein the persulfate oxidizer is one that is more efficient.

In one embodiment, the radiation dose of the urea oxidation decomposer Oxi-RU is 240mJ/cm ² The reaction was preceded by a 2:1 adding H ₂ O ₂ And Na (Na) ₂ S ₂ O ₈ The TOC of the pretreated water can be reduced from 86 mug/l to 12.9 mug/l by mixing the water with the water, 5.2 mug/l after an ion exchange tower and 19.6 mug/l by reducing the carbon amide (CH 4N 2O) from 202 mug/l, the low molecular organic matter treatment efficiency is 85%, the urea removal rate is 90%, and the TDS increment is 62mg/l, which is obviously higher than that of the common UV/H due to the coupling of a dual-wavelength alloy mercury lamp and two oxidants ₂ O ₂ About 20% urea removal.

A set of activated carbon absorption tower (GAC) is designed behind the urea oxidation decomposer Oxi-RU, can effectively absorb hydrophobic neutral, hydrophobic acidic and hydrophobic weak acidic organic matters with the molecular weight of 500-3000 Da, and has better effect on absorbing and removing a large amount of residual hydrogen peroxide in the produced water of the urea oxidation decomposer Oxi-RU.

The filler in the activated carbon absorption tower is preferably a physically modified GAC filter material.

The pH is a key factor affecting the rate of the GAC quenching reaction. Typically pH<7.5 environmental H ₂ O ₂ Is stable and not easy to be removed, and has pH value>At 7.5, the preferred ph=8 to 9.5, h ₂ O ₂ More easily dissociate into OH and OH ^- But quenched.

Temperature is also a critical factor affecting the rate of the GAC quenching reaction. Quenching of H with GAC ₂ O ₂ The temperature-affected characteristic is that the outlet water temperature of the secondary side of the first heat exchanger HEX-1 arranged in front of the Oxi-RU is set to be 25-28 DEG, which not only prevents the summer roomThe condensation phenomenon possibly occurring in the metal cylinder bodies such as the filter, the reactor, the absorption tower, the exchange tower and the like due to the temperature rise can also effectively accelerate the H in the active carbon absorption tower ₂ O ₂ The quenching reaction rate of the GAC is improved, and the purpose of improving the GAC quenching efficiency is finally achieved.

The water produced by the GAC directly enters the composite ion exchange tower. The composite ion exchange tower consists of Yang Da and a negative tower, the conductivity of produced water can be generally smaller than 5 mu S/cm through double-tower ion exchange and charge adsorption, the removal efficiency of TOC can also reach 90%, and the removal rate of low-molecular organic matters can reach 61-71%.

The primary desalted water is stored by a pre-desalted water tank and is supplied to a reverse osmosis device. The reverse osmosis treatment can achieve 94% of total removal rate of suspended organic carbon, colloidal organic carbon and dissolved organic carbon contained in total organic carbon in NOM.

However, for some ultra-low molecular weight compounds in reuse or regeneration water, such as isopropyl alcohol IPA, methanol, urea, etc., only 15% removal is obtained because reverse osmosis membranes have poor rejection capability for hydrophilic low molecular organics without surface charges at neutral pH.

The deep desalting section adopts a brand new combination of processing units, namely MB+U-PSA+MDG, after the traditional regeneration mixed bed MB finishes deep desalting, a first mixed photolysis absorber U-PSA is designed, the device effectively and further removes TOC, boron, silicon, carbon dioxide and other weakly ionized impurities in MB produced water, and dissolved gas generated by photolysis organics is thoroughly removed by utilizing a vacuum membrane degassing device MDG, so that the purposes of comprehensively and deeply reducing all salt electrolytes, low-molecular organics, weakly ionized impurities, dissolved oxygen and bacteria to quasi-ultrapure water quality indexes are achieved.

As shown in fig. 2, the first hybrid photolytic absorber U-PSA includes:

At least one first housing 11, which is a transparent heat-insulating hollow closed structure;

at least one radiation source 12, the radiation source 12 being arranged within the hollow enclosure to form a vacuum radiation cavity 13;

a second housing 14 surrounding the at least one first housing 11;

a connection cover 15 provided on the top of the second housing 14;

the lower supporting hole plate 16 is arranged at the bottom of the second casing 14, the lower supporting hole plate 16, the inner wall of the second casing 14, the outer wall of the first casing 11 and the connecting cover 15 form a first reaction cavity 17, the first reaction cavity 17 forms a photolysis zone 171 under the irradiation of the vacuum radiation cavity 13, water to be purified enters the first reaction cavity 17 from the lower supporting hole plate 16 and flows out from an outflow hole 199 at the upper part of the second casing to form a water flow channel, and the water flow channel at least partially overlaps with the photolysis zone 171 to photocatalytically oxidize the water to be purified to form first treated water;

a third housing 18 having a bottom wall 181 below the lower support orifice plate 16 and a side wall 182 extending upwardly from the bottom wall 181, the side wall 182 enclosing an opening, the side wall 182 surrounding the second housing 14;

a top cover 183 detachably covering the opening;

A first orifice plate 184, one end of which is fixed to the side wall 182 and the other end of which is fixed to the outer wall of the second housing 14, wherein the first orifice plate 184, the side wall 182, the outer wall of the second housing 14 and the top cover 183 form a sealed chamber 186, and the first treatment water enters the sealed chamber 186 from the first reaction chamber 17;

a second orifice plate 185, one end of which is fixed to the side wall 182, and the other end of which is fixed to the outer wall of the second housing 14, wherein the second orifice plate 185, the side wall 182, the outer wall of the second housing 14 and the bottom wall 181 form a water collecting cavity 187;

a second reaction chamber 188 is formed by the first orifice plate 184, the side wall 182, the outer wall of the second housing 14, and the second orifice plate 185.

The upper part of the second reaction chamber 188 is filled with a boron absorbent to form a complex reaction zone 191, the lower part of the second reaction chamber 188 is filled with a positive charge absorbent to form a positive charge absorption zone 192, and the first treatment water from the sealing chamber 186 sequentially removes boron in the complex reaction zone 191 and weak acid salt in the positive charge absorption zone 192;

an inlet 19 penetrating through the bottom wall 181 and communicating with the first reaction chamber 17;

an outflow port 193 penetrating the sidewall 182 and communicating with the water collection chamber 187.

In the preferred embodiment of the first hybrid photolytic absorber U-PSA, the first housing 11, the second housing 14, and the third housing 18 are centrally symmetric about a common central axis.

The purification scheme of the first hybrid photolytic absorber U-PSA includes the steps of,

the water to be purified (primary pure water) comes from the mixed bed system MB and the flow rate is adjustable into the inflow port 19.

The water to be purified enters the first reaction cavity 17 through the inflow port 19, and the water-soluble organic matters in the water are degraded in the photolysis zone 171 of the first reaction cavity 17 from bottom to top to form first treated water;

the first treatment water enters the sealing cavity 186 from the first reaction cavity 17, and sequentially removes boron in the complexation reaction zone 191 and weak acid salt in the positive electric adsorption zone 192 to form secondary pure water, wherein the boron is reduced to below 1ng/l, and the TOC concentration is reduced to 1-2 mug/l;

secondary deionized water is collected in the water collection chamber 187 and is directed out through the outflow port 193.

In one embodiment, the first hybrid photolytic absorber U-PSA is a highly integrated cylindrical sleeve reactor consisting of vacuum radiation chamber 13, first reaction chamber 17, second reaction chamber 188, sealed chamber 186, and water collection chamber 187, functionally divided into radiation zone, photolysis zone 171, complexation reaction zone 191, positively charged adsorption zone 192, transition zone 189, and collection zone 195. As shown in fig. 2, the radiation source 12 is mounted in a first housing 11, such as a first cylindrical housing. The first cylindrical shell has the function of preventing the heat of the light source from being taken away by the treated water, so that the temperature in the vacuum radiation cavity 13 is not too low to influence the luminous efficiency, and the heat preservation function also has the effect of stabilizing the ultraviolet light output.

The radiation source 12 may employ a variety of UV light excitation devices, at least dual wavelength low pressure high intensity mercury vapor or low pressure mercury in the first hybrid photolysis absorber U-PSAJi Huguang discharge sources, and more preferably, dual wavelength low pressure amalgam arc discharge sources. In a preferred embodiment of the present utility model, the first cylindrical housing is made of high purity quartz SiO having excellent optical transmittance for UV light ₂ The glass is preferably made of high-purity synthetic fused quartz materials, and the requirement of the transmittance of more than 90% is met.

The second cylindrical shell adopts a three-layer structure at least, and is provided with a low-light-transmittance quartz layer, a shielding reflecting layer and a metal-free isolating layer, preferably, a layer of metal film (a second surface mirror) is plated on the outer surface of the low-light-transmittance quartz layer by utilizing a vacuum evaporation method, further preferably, a VUV (vacuum ultraviolet) hardening metal film is adopted to form a first surface mirror, so that the reflection loss of multiple interfaces caused by Fresnel reflection is avoided, and the reflectivity can be effectively improved.

In one embodiment, a water flow channel is formed between the second housing 14, such as a second cylindrical housing, and one or more first cylindrical housings, and a connection cover 15 and a lower support orifice plate 16, referred to as a first reaction chamber 17, are provided at the upper and lower portions. The water produced by the mixed bed system MB firstly enters the first reaction cavity 17, in a photolysis zone 171 of which the continuous flow is formed from bottom to top in the first reaction cavity 17, VUV is strongly absorbed by water molecules to generate hydroxyl free radicals and superoxide free radicals, and the hydroxyl free radicals and residual soluble pollutants in the flowing water undergo addition reaction and hydrogen extraction reaction, so that the molecular structure of DOM is greatly degraded.

The deep desalted water after photolysis flows into the sealing cavity 186 at the top to form a transition zone 189 connected with the adsorption zone, and the space between the photooxidizer and the adsorption tower (or the deep desalted tower) in the prior art is obviously reduced structurally, so that micro-pollution accumulation and power loss caused by separation of process materials due to the transmission distance are effectively reduced.

In one embodiment, a complex reaction region 191 and a positively charged adsorption region 192 are formed between the third housing 18, such as a third cylindrical housing, and the second cylindrical housing, depending on the absorbent material, and the space in which these two regions are located is referred to as a second reaction chamber 188.

Water enters the second reaction chamber 188 through the sealing chamber 186, and firstly passes through the absorbing material at the upper part of the complexing reaction zone 191 from top to bottom, so that the weakly ionized impurity boron in the water and the absorbing material undergo strong complexing reaction. The upper absorbing material is boron absorbent, and can be chemically adsorbed with boron in water to form a ring-shaped esterified substance with stable structure, so as to achieve the aim of firmly adsorbing the boron and preventing the boron from falling off.

The complexing reaction is reversible reaction, and after the absorbing material is saturated, the complexed boric acid can be desorbed by an in-vitro eluting mode.

In the second reaction chamber 188 formed between the third cylindrical housing and the second cylindrical housing, H is not easily removed in RO and MB due to weak ionization ₃ BO ₃ The initial leakage concentration in this reaction zone was reduced to very high levels of less than 0.5 ng/l. The boron-depleted water then passes directly into a positively charged adsorption zone 192 located in the lower portion of the complexation reaction zone 191. The positively charged adsorption zone 192 is in intimate engagement with the complexation reaction zone 191 filled with a different absorbent material. The absorbent material filled in the positively charged adsorption zone 192 may be, for example, a strong adsorbent having or mixed with a functional group having a quaternary ammonium group and having a positive charge, and may have a stronger adsorption function on small-molecular organic matters in water. The TOC concentration of the U-PSA outlet 193 is eventually reduced to 1-2. Mu.g/l by a synergistic reaction such as adsorption exchange.

Another important function of the positively charged adsorption zone 192 is to adsorb the polymer eluted from the boron adsorbent in the complexing reaction zone 191, controlling the increased polymer concentration to 1 μg/l or even lower.

The lower portion of positively charged adsorption zone 192 is separated from collection zone 195 by a support baffle (i.e., a second orifice plate), and collection zone 195 is positioned within collection chamber 187 below the baffle. Above the partition, one or more tower-shaped water distributors 194 are positioned to collect the positively charged adsorption zone 192 process water into the water collection chamber 187 while isolating the adsorbent particle beads. Preferably, an embedded cylindrical water distributor 194 is adopted, a layer of polyhexamethylene adipamide filter screen is fixed on the inner side of a polypropylene framework support, and the aperture is 60-80 meshes, so that the problems that a traditional water distribution cap is aged and broken and an exchanger is leaked are solved, and a common post-arranged resin catcher is also used to save a pipeline device. The water collecting cavity 187 below the partition plate is connected with the water outlet flange and the water discharge pipeline and is sealed and isolated with the water inlet pipe.

In the first mixed photolysis absorber U-PSA, all the overflow surfaces and water passing devices, including inflow pipes, cavities, partition boards, channels, water collectors and the like, which are contacted with water are designed to be high-molecular polymer materials or quartz materials, and the alloy steel materials of the traditional reactor and exchange tower are abandoned, so that the design purpose of demetallization or metal minimum of the whole equipment is achieved.

Based on the influence of the main inorganic anions on the TOC degradation efficiency, the first mixed photolysis absorber U-PSA is made and then placed in the process design consideration of MB, so that the catalytic oxidation efficiency of the photolysis zone 171 on TOC is improved.

In the design of the polishing system, the application continues to use a completely new combination of processing units, namely the combination of U-PMB+MDG+UF. The U-PMB catalytic mixed photolysis absorber integrates the treatment technology of various devices such as photocatalytic oxidation, weak acid and acid salt absorption, catalytic quenching of free radical composite oxidant, fine polishing of trace electrolyte and the like. Through the treatment of the U-PMB, most technical indexes of the POD end of the ultrapure water can meet the design standard and the process requirement.

As shown in fig. 3 to 5, the catalytic hybrid photolysis absorber U-PMB includes,

at least one first housing 21, which is a transparent, heat-insulating hollow closed structure;

At least one radiation source 22, the radiation source 22 being arranged within the hollow enclosure to form a vacuum radiation cavity 23;

a second housing 24 surrounding the at least one first housing 21;

a connection cover 25 provided on the top of the second housing 24;

the lower supporting hole plate 26 is arranged at the bottom of the second shell 24, the lower supporting hole plate 26, the inner wall of the second shell 24, the outer wall of the first shell 21 and the connecting cover 25 form a first reaction cavity 27, the first reaction cavity 27 forms a photolysis zone 271 under the irradiation of the vacuum radiation cavity 23, water to be purified enters the first reaction cavity 27 from the lower supporting hole plate 26 and flows out from an outflow hole 299 at the upper part of the second shell 24 to form a water flow channel, and the water flow channel at least partially overlaps with the photolysis zone 271 to photocatalytically oxidize water to be purified to form first treated water; the first treated water includes a secondary oxidant;

a third housing 28 having a bottom wall 281 below the lower support orifice 26 and a side wall 282 extending upwardly from the bottom wall 281, the side wall 282 enclosing an opening, the side wall 282 surrounding the second housing 24;

a top cover 283 detachably covering the opening;

a first orifice plate 284, one end of which is fixed to the side wall 282 and the other end of which is fixed to the outer wall of the second housing 24, wherein the first orifice plate 284, the side wall 282, the outer wall of the second housing 24 and the top cover 283 form a sealed cavity 286, and the first process water enters the sealed cavity 286 from the first reaction cavity 27;

A second orifice plate 285, one end of which is fixed to the side wall 282 and the other end of which is fixed to the outer wall of the second housing 24, wherein the second orifice plate 285, the side wall 282, the outer wall of the second housing 24 and the bottom wall 281 form a water collecting chamber 287;

a second reaction chamber 288 formed by the first orifice plate 284, the side wall 282, the outer wall of the second housing 24, and the second orifice plate 285.

The second reaction chamber 288 is sequentially filled with a positive charge adsorbent, a metal catalyst or a metal oxide catalyst, and an ion exchanger from top to bottom to form a positive charge adsorption region 291, a catalytic reaction region 292, and an ion polishing region 293, and the first treated water from the sealing chamber 286 sequentially removes weakly acidic compounds, secondary oxidants, soluble ions, and other organic impurities in the positive charge adsorption region 291, the catalytic reaction region 292, and the ion polishing region 293 to form ultrapure water.

The catalytic mixed photolysis absorber U-PMB also comprises,

an inlet 29 penetrating through the bottom wall 281 and communicating with the first reaction chamber 27;

an outlet 294 is provided through the side wall 282 and communicates with the water collection chamber 287.

In the preferred embodiment of the catalytic hybrid photolytic absorber U-PMB, the first housing 21, the second housing 24 and the third housing 28 are of a centrosymmetric structure with a concentric axis.

The second orifice plate 285 is provided with at least one tower-shaped water distributor 295, which collects the treated water after polishing in the ion polishing zone into a water collection chamber 287 and isolates the ion exchanger.

The tower-shaped water distributor 295 is an embedded cylindrical water distributor, and a layer of polyhexamethylene adipamide filter screen with the aperture of 60-80 meshes is fixed on the inner side of a polypropylene framework support.

The purification process of the catalytic mixed photolysis absorber U-PMB comprises the following steps,

the water to be purified (secondary pure water) comes from the heat exchanger and the flow rate is adjustable into the inflow port 29;

the water to be purified enters the first reaction cavity 27 through the inflow port 29, and in a photolysis zone 271 of which the first reaction cavity 27 forms continuous flow from bottom to top, the water-soluble organic matters are further degraded to form first treated water;

the first treatment water enters the sealing cavity 286 from the first reaction cavity 27, the first treatment water sequentially removes weak acid compounds in the positive electric adsorption area 291, quenches the secondary oxidant in the catalytic reaction area 292 and reduces trace metals, nonmetallic ions and soluble low molecular organic matters in the ion polishing area 293 to form ultrapure water, wherein the trace metals are reduced to below 0.2ng/l, preferably, the concentration of TOC is reduced to below 1 mug/l, and the concentration of TOC is reduced to below 0.05 ng/l;

Ultrapure water is collected in the water collection chamber 287 and is led out through the outflow port 294.

In one embodiment, the catalytic hybrid photolysis absorber U-PMB employs a cylindrical sleeve reactor consisting of a vacuum radiation chamber 23, a first reaction chamber 27, a second reaction chamber 288, a sealed chamber 286, and a water collecting chamber 287, functionally divided into a radiation zone, a photolysis zone 271, a positively charged adsorption zone 291, a catalytic reaction zone 292, an ion polishing zone 293, a transition zone 289, and a collection zone 296. As shown in fig. 3, the radiation source 22 is mounted in a first housing 21, such as a first cylindrical housing. The first cylindrical shell has the function of preventing the heat of the light source from being taken away by the treated water, so that the temperature in the vacuum radiation cavity 23 is not too low to influence the luminous efficiency, and the heat preservation function also has the effect of stabilizing the ultraviolet light output.

The radiation source 22 may be a variety of UV light excitation devices, and should be at least a dual wavelength low pressure high intensity mercury vapor or low pressure amalgam arc discharge source in the catalytic hybrid photolysis absorber U-PMB, and more preferably, a dual wavelength low pressure amalgam arc discharge source. In a preferred embodiment of the present utility model, the first cylindrical housing is made of transparent quartz SiO having excellent optical transmittance for UV light ₂ The prepared material has hydroxyl content less than or equal to 5 mug/g, is preferably prepared from high-purity synthetic fused quartz material, and needs to meet the requirement of transmittance more than 90%.

A water flow channel is formed between a second housing 24, such as a second cylindrical housing, and one or more first cylindrical housings, and a connection cover 25 and a lower support orifice 26, referred to as a first reaction chamber 27, are provided at upper and lower portions. The secondary pure water in the pure water storage tank PWT passes through the second heat exchanger 321, firstly enters the first reaction cavity 27, and in the photolysis zone 271 where the first reaction cavity 27 forms continuous flow from bottom to top, VUV is strongly absorbed by water molecules to generate hydroxyl free radicals and superoxide free radicals, and the hydroxyl free radicals and the residual soluble pollutants in the overflow water undergo addition reaction and hydrogen extraction reaction, so that the molecular structure of DOM is further greatly degraded.

The second cylindrical shell adopts at least three layers of structures, namely, a low-light-transmission quartz layer 241, a shielding reflection layer 242 and a metal-free isolation layer 243, preferably, a layer of metal film (a second surface mirror) is plated on the outer surface of the low-light-transmission quartz layer 241 by utilizing a vacuum evaporation method, further preferably, a first surface mirror is formed by adopting a VUV (vacuum ultraviolet) hardening metal film, so that the reflection loss of multiple interfaces caused by Fresnel reflection is avoided, and the reflectivity can be improved more effectively.

The deep desalted water after photolysis flows into the sealing cavity 286 at the top to form a transition region 289 connected with the adsorption region, which structurally obviously reduces the equipment spacing between the photooxidizer and the weak acid adsorption tower or the mixed ion exchange tower in the prior art, and effectively reduces micro-pollution accumulation and power loss caused by separation of process materials due to the transmission distance.

Between the third housing 28 of the third cylindrical housing and the second cylindrical housing, a positive electric adsorption region 291, a catalytic reaction region 292, and an ion polishing region 293 are formed depending on the absorption material, and the space in which these three regions are located is referred to as a second reaction chamber 288. All the overflow surfaces and water passing devices, including the inlet 29, the cavity, the upper and lower support pore plates 26, the channels and the like, which are contacted with water are designed to be made of high polymer materials or quartz materials, and the alloy steel materials of the traditional reactor and exchange tower are abandoned, so that the design purpose of demetallization or metal minimum of the whole equipment is achieved.

In the first reaction chamber 27, after VUV/UV irradiation, the water molecules undergo homolytic cleavage and ionization, and the compound reaction of free radicals is to generate H ₂ O ₂ Is the main route of (3). Excess concentration H ₂ O ₂ Does not quench itself in the photodecomposition zone 271, and enters the post-polishing CP apparatus according to the existing process flow, with the effect of "resin degradation".

The present utility model provides for the catalytic reaction zone 292 to convert the residual H produced in the photolysis zone 271 ₂ O ₂ The concentration is controlled to be 5. Mu.g/l or less, preferably less than 1. Mu.g/l.

The absorbent material packed in the catalytic reaction zone 292 may be, for example, a complex phase metal catalyst containing a transition metal as a complex; preferably, a noble metal nanoparticle immobilized high molecular polymer catalyst is selected, and more preferably, a nano alloy composite particle catalyst is selected.

The secondary pure water quenched by the secondary oxidant through the catalytic reaction area 292 enters the ion polishing area 293 at the lower part, and the absorption material filled in the ion polishing area 293 can be, for example, two ion exchangers respectively provided with alkaline and acid groups and pre-mixed, and the ion polishing area 293 is tightly connected with the catalytic reaction area 292 by filling different absorption materials. In the ion polishing region 293, trace metal ions, nonmetallic ions and soluble low-molecular organic matters in the secondary pure water are deeply removed and absorbed, so that most water quality indexes of the POD end of the ultrapure water meet the requirements at the outflow port 294.

The catalytic hybrid photolytic absorber U-PMB post-equipment includes a second fine filter 322, a second vacuum membrane degasser 307, and a terminal ultrafilter 308. Further, the catalytic hybrid photolysis absorber 306, the second fine filter 322, the second vacuum membrane degasser 307 and the terminal ultrafilter 308 are sequentially communicated in the water flow direction. The second vacuum membrane degasser 307 efficiently removes dissolved gas leaked from the catalytic type mixed photolysis absorber U-PMB by using a membrane degassing technology in a nitrogen and vacuum combined purging mode, so that residual dissolved oxygen reaches a level less than or equal to 1 mug/l, and finally all bacteria and microparticle impurities are removed to be less than 0.05 mu m (microparticles more than 0.05 mu m are less than 0.05 pcs/ml) by the terminal ultrafilter 308.

In a preferred embodiment of the nano integrated circuit cleaning water preparing system, the primary pure water system further comprises a cartridge filter SF and an RO water tank ROT, and the reverse osmosis device RO is disposed between the cartridge filter SF and the RO water tank ROT in a water flow direction.

In a preferred embodiment of the system for preparing nano integrated circuit cleaning water, the deep desalting system further comprises a mixed ion exchange tower MB, a first fine filter 316 and a first vacuum membrane degassing device MDG-1 which are sequentially connected in the water flow direction, and the first mixed photolysis absorber U-PSA is arranged between the mixed ion exchange tower MB and the first fine filter 316.

In a preferred embodiment of the nano integrated circuit cleaning water preparation system, the polishing system further comprises a pure water storage tank PWT, a second heat exchanger HEX-2, a second fine filter RF-2, a second vacuum membrane degassing device MDG-2 and a terminal ultra-filter UF which are sequentially connected in the water flow direction, and a catalytic type mixed photolysis absorber U-PMB is arranged between the second heat exchanger HEX-2 and the second fine filter RF-2.

In a preferred embodiment, a process flow of a system for preparing nano-integrated circuit cleaning water is: step S1: the raw water is driven by a pump to pass through a first heat exchanger HEX-1 and a multi-medium filter MMF by a production water pool CWT, is injected into a filtering water pool FWT, removes most suspended matters in the water, reduces SDI to below 5, and raises the temperature.

Step S2: after the water is subjected to turbidity removal and temperature rise, the water enters a high-grade oxidation system through a filter water tank FWT, the high-grade oxidation system comprises a urea oxidation decomposer Oxi-RU and an activated carbon absorption tower GAC, the photolysis treatment of organic matters and the absorption quenching (comprising dechlorination treatment) of oxidants are completed in the high-grade oxidation system, so that most of colloid, microorganisms, NDOM (non-soluble organic matters), bacteria and the like in the water are removed, and then primary desalting is carried out through a composite ion exchange tower SC+SA to form shallow desalted water, and the shallow desalted water is collected in a pre-desalted water tank DIT.

Step S3: the shallow desalted water in the pre-desalted water tank DIT is subjected to power lifting and is supplied to a cartridge filter SF and a reverse osmosis device RO of a primary pure water system, the osmotic pressure of a semipermeable membrane of the reverse osmosis device is overcome under the high pressure effect of the shallow desalted water, most of dissolved salt, colloid, macromolecular organic matters, microparticles, silicon dioxide and a small amount of boric acid are filtered, fresh water after passing through the membrane becomes primary pure water, the primary pure water is collected in the RO water tank ROT, and concentrated water which does not pass through the membrane is recovered to a filtering water tank FWT.

Step S4: the primary pure water in the RO water tank ROT is sequentially processed by a mixed ion exchange tower MB, a first mixed photolysis absorber U-PSA, a first fine filter RF-1 and a first vacuum membrane degassing device MDG-1 through power lifting, after dissolved salt is further removed by the mixed ion exchange tower MB, total organic carbon, weakly ionized impurities boron, silicon, carbon dioxide and the like are deeply removed by the mixed photolysis absorber U-PSA, and then most of oxygen and carbon dioxide are removed by the first vacuum membrane degassing device to form secondary pure water which is close to the quality of the ultrapure water, and the secondary pure water is sealed in a pure water storage tank PWT.

Step S5: the pure water storage tank PWT for storing the secondary pure water forms a closed circulation LOOP with a LOOP water supply and return pipeline leading to POE or POU Filter and polishing system treatment equipment. In the treatment section of the polishing system, after the temperature of the secondary pure water is regulated in a second heat exchanger HEX-2, trace metal ions, weakly ionized impurities and low molecular organic matters which are strictly controlled in the scheme are respectively removed to extremely high limit values of indexes of ppq level (gigabit), ppt level (trillion) and ppb level (billion), meanwhile, the nano particle catalyst in the U-PMB is utilized to control the free radical composite oxidant to be in the sub ppb level, and then the soluble gas and the fine particles in the residual water are finally removed to the highest standard range of the sub ppb level and the nano level required by the prior process through a second fine filter RF-2, a second vacuum membrane degassing device MDG-2 and a terminal ultra-filter UF.

Finally, it should be noted that: the described embodiments are intended to be illustrative of only some, but not all, of the embodiments disclosed herein and, based on the embodiments disclosed herein, all other embodiments that may be made by those skilled in the art without the benefit of the teachings herein are intended to be within the scope of this application.

While certain exemplary embodiments of the present utility model have been described above by way of illustration only, it will be apparent to those of ordinary skill in the art that modifications may be made to the described embodiments in various different ways without departing from the spirit and scope of the utility model. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive of the scope of the utility model, which is defined by the appended claims.

Claims

1. A system for preparing nano integrated circuit cleaning water is characterized by comprising,

the pre-desalting system performs pre-desalting on raw water to obtain shallow desalted water, and comprises a urea oxidation decomposer (300) using an advanced oxidation technology, an active carbon absorption tower (301) for absorbing residual oxidant and a compound ion exchange tower (302) for pre-desalting, which are sequentially connected in the water flow direction;

The primary pure water system is connected with the pre-desalting system and used for performing membrane method desalting on the shallow desalted water to obtain primary pure water, and the primary pure water system comprises a reverse osmosis device (303);

the deep desalting system is connected with the primary pure water system and is used for deep desalting the primary pure water to obtain secondary pure water, and comprises a mixed ion exchange tower (304) for removing soluble salt, a first mixed photolysis absorber (305) for removing organic carbon and weakly ionized impurities and a first vacuum membrane degasser (318) which are sequentially connected in the water flow direction;

the polishing system is connected with the deep desalting system and polishes the secondary pure water to obtain nano-process integrated circuit cleaning water, and comprises a catalytic mixed photolysis absorber (306) for polishing, a second vacuum membrane degassing device (307) for removing dissolved gas and an ultra-filter (308) for removing microparticles, which are sequentially connected in the water flow direction.

2. The system for preparing nano integrated circuit cleaning water according to claim 1, wherein the pre-desalting system further comprises a production water tank (309), a first heat exchanger (310), a multi-medium filter (311), a filtering water tank (312) and a pre-desalting water tank (313) which are sequentially connected in the water flow direction, wherein the urea oxidative decomposer (300) is connected to the rear end of the filtering water tank (312), and the composite ion exchange tower (302) is connected to the front end of the pre-desalting water tank (313).

3. The system for preparing nano-integrated circuit cleaning water according to claim 1, wherein the primary pure water system further comprises a cartridge filter (314) and an RO water tank (315), and the reverse osmosis device (303) is disposed between the cartridge filter (314) and the RO water tank (315) in the water flow direction.

4. The system for preparing nano-integrated circuit cleaning water according to claim 1, wherein the deep desalting system comprises a mixed ion exchange tower (304), a first fine filter (316) and a first vacuum membrane degasser (318) which are sequentially connected in the water flow direction, and the first mixed photolysis absorber (305) is arranged between the mixed ion exchange tower (304) and the first fine filter (316).

5. The system for preparing nano-integrated circuit cleaning water according to claim 1, wherein the polishing system comprises a pure water storage tank (320), a second heat exchanger (321), a second fine filter (322), a second vacuum membrane degasser (307) and a terminal ultra-filter (308) which are sequentially connected in the water flow direction, and the catalytic hybrid photolysis absorber (306) is disposed between the second heat exchanger (321) and the second fine filter (322).

6. A system for preparing nano-integrated circuit cleaning water according to claim 1, characterized in that the radiation light source of the urea oxidative decomposer (300) is a UV or VUV mercury vapor or low pressure high intensity amalgam arc discharge light source.

7. The system for preparing nano-integrated circuit cleaning water according to claim 1, wherein the first hybrid photolysis absorber (305) or the catalytic hybrid photolysis absorber (306) comprises:

a second housing surrounding the at least one first housing;

the connecting cover is arranged at the top of the second shell;

A top cover detachably covering the opening;

8. The system for preparing nano-integrated circuit cleaning water according to claim 7, further comprising,

the inflow port penetrates through the bottom wall and is communicated with the first reaction cavity;

9. The system for preparing nano-integrated circuit cleaning water according to claim 7, wherein the second orifice plate is provided with at least one tower-shaped water distributor.

10. The system for preparing nano-integrated circuit cleaning water according to claim 7, wherein the first housing, the second housing and the third housing are of a centrosymmetric structure with respect to a central axis.