CN1189787A - Point-of-use ammonia purifation for electronic component manufacture - Google Patents

Abstract

Highly purified HCl for use in semiconductor manufacturing is prepared on-site by drawing HCl vapor (12) from a liquid HCl reservoir (11), and scrubbing (17) the filtered vapor (15) in a low-pH aqueous scrubber (17).

Description

Semiconductor machining is with the in situ preparation of ultra-pure hydrochloric acid

Background of invention and general introduction

The present invention relates to provide the system and the method for ultra-pure hydrochloric acid for the semiconductor manufacturing.

Pollute all in all thing of normally in the integrated circuit manufacturing, being concerned about.Most of step in the modern integrated circuits manufacturing is this class or that class cleaning step; These cleaning steps may need to remove accessory substance, native oxide of organic pollution, metal pollutant, photoengraving agent (or its inorganic residue), etching etc.

According to the data of nineteen ninety-five, the expense of a cover making apparatus in early stage (IC wafer manufacturing works) is usually greater than 1,000,000,000 dollars, and wherein major part is used for the measure of particle control, cleaning and pollution control.

An important source that pollutes is the impurity in the process chemical.Because it is like this frequent and important cleaning, and is very undesirable owing to clean the chemical pollution that causes.

In one of medium-term and long-term technology change that takes place of semiconductor machining is to do variation between processing and the wet processing (and attempt carry out variation).In doing processing, have only gaseous reactant or plasma phase reaction thing to contact with wafer.In wet processing, various liquid reagents are used for different purposes, as etching silicon dioxide or remove natural oxide skin(coating), remove organic substance or trace organic pollution, remove metal or micro quantity organic pollutant, etch silicon nitride, etch silicon.

Though plasma etching has many attracting abilities, it is not suitable for cleaning.Also there is not the easy chemical method that gets to be used for removing some least desirable impurity, as gold.Therefore, for modern semiconductors processing, wet-cleaning is very important; And in a foreseeable future, may be still like this.

Plasma etching is undertaken by in position using the photoengraving agent, and high-temperature step can not directly be adopted in its back.Otherwise etching agent is peeled off, then essential the cleaning.

The material that cleaning must be removed can comprise: photoengraving agent residue (organic polymer); Sodium; Alkaline-earth metal (as calcium or magnesium); And heavy metal (as gold).Wherein many materials can not form the volatility halides, so plasma etching can not be taken away them.Need with the wet chemistry method cleaning.

Consequently, the purity of process chemical is so unimportant when plasma etching, because plasma etch step always has cleaning step later on before high-temperature step is carried out, cleaning step can be before these pollutants of high-temperature step effect be removed these harmful pollutants from the surface.But it is much important that the purity of liquid chemical is wanted, since common in the collision rate on the semiconductor surface than high 1,000,000 times in plasma etching, and because directly follow high-temperature step behind the liquid cleaning step.

But wetting is processed with main shortcoming, i.e. an ionic soil.The integrated circuit structure thing only uses seldom several dopant species (boron, arsenic, phosphorus and also have antimony sometimes), to form required P type and N type doped region.But many other material kinds also are active adulterant on electronics, and they are very undesirable pollutants.Wherein many pollutants have injurious effects, for example are lower than 10 in concentration ¹³Individual/cm ³The time just produce high junction leakage, and some more undesirable pollutants can be gone in the silicon by liquates; Promptly under silicon and occasion that the aqueous solution contacts, the equilibrium concentration of pollutant in silicon is than the height in solution.And some more undesirable pollutants have very high diffusion coefficient, and consequently such alloy is introduced any part of silicon wafer and all tended to make these Pollutants Diffusion to entire wafer, comprises that these pollutants will cause the semiconductor junction of electric leakage.

Therefore, all liq solution all metal ions that is used on the semiconductor wafer preferably has extremely low content.Preferably, all metals concentration altogether should be less than 300ppt (hundreds of millions (trillion)/one); And for any metal, concentration should be less than 10ppt, and the smaller the better.And, the also all essential control of pollution that causes because of anion and cation.(some anion have bad influence, and for example complexation of metal ions can make metallic atom or the ion mobility in silicon crystal lattice descend.)

Early stage, manufacturing equipment generally included the on-the-spot purification system of preparation high purity water (being called " DI " water, i.e. deionized water).But the process chemical that will obtain required purity is difficult more.

Female case application discloses a kind of method for preparing ultra-pure ammonia in the on-the-spot system on semiconductor wafer production ground: extract the ammonia steam from the liquid ammonia reservoir out; Make the ammonia steam pass through microstrainer; And wash filtered steam with high pH value purified water (preferred deionized water, it is crossed with the ammonia mobile equilibrium).This discovery can make business level ammonia be transformed into and be applicable to the enough highly purified ammonia of having of high-accuracy manufacturing, and does not need traditional destilling tower.The ammonia steam is used as the single-stage distillation from the extraction of feed reservoir itself, nonvolatile impurity and high boiling impurity have been removed, as oxide, carbonate and the hydride of alkali metal and alkaline-earth metal, the halide of transition metal and hydride, and high-boiling hydrocarbon and halohydrocarbon.Thought the reactive volatile impurity that can in business level ammonia, find in the past, need distill as the hydride of the hydride of some transition metal halide, III-th family metal and halide, some IV family metal and halide and halogen and to remove, and find now, they can be removed by scrubbing, reach the degree that is suitable for high-accuracy operation.This is a very abnormal discovery, because scrubbing technology tradition is used to remove constant impurity, rather than is used to remove trace impurity.

It is that seldom see in the various industrial technologies or unique that semiconductor is made required extremely pure content.Under so extremely pure content, the processing of chemicals was undesirable (certainly, though this point can not be avoided fully) originally.Must reduce ultrapure chemicals as far as possible and be exposed to (particularly in the environment that the workman exists in addition) in the air.Such exposure has the risk of introducing particle, pollutes thereby produce.The shipping of ultrapure chemicals in the container of sealing also is undesirable, because in manufacturer or in all intrinsic very high pollutant risk in user place.And nd pollutant may damage the wafer of a large amount of costlinesses.

Because there are many mordant and/or virose chemicals to be used for semiconductor machining usually, the supply place of reagent all makes the workman location with early stage usually and separates.Be used for ultra-pure gas and liquid the pipeline system construction and be maintained in semi-conductor industry and finely understood, majority of gas and liquid just can be transported to the wafer manufacturing place from (perhaps even same place) Anywhere of identical building like this.

The application discloses system and the method at the ultrapure chemicals of semiconductor fabrication factory in situ preparation, so that they can directly deliver to the use point with pipeline.Disclosed system is very compact device, and they can make (or in adjacent building) in the identical building with early stage, so that can avoid handling.

Hydrochloric acid

The important semiconductor machining chemicals of one class is the HCl of gaseous form and moisture form.Liquid hydrochloric acid also is widely used in the sour cleaning part in the standard RCA cleaning.

As mentioned above, female case application discloses method and the system for preparing ultra-pure ammonia.Have now found that the improvement of these methods and system can be used for preparing ultra-pure HCl.

Raw material is the anhydrous HCl of business level.Provide first purification step by simple vaporization.(vapour pressure at 70 following HCl is 613 pounds/inch ², and be 1185 pounds/inch under 124.5 °F ², so this vapour pressure is always to extract out from big basin abundant discharge pressure is provided.) preferred HCl steam directly extracts out from basin.(in another embodiment, liquid HCl shifts from big basin in batches, and vaporizes in vaporizer under controlled temperature and pressure.)

The preparation of hydrochloric acid

Now can purified gaseous state HCl is soluble in water, make concentrated hydrochloric acid.

The in situ preparation of ultrapure mixing cleaning solution

The application discloses at the wafer-fabs scene, is mixed cleaning solution in the same place by each composition preparation of ultrapureization by itself, as the method for RCA acid cleaning solution and RCA alkali cleaning solution.

RCA cleans and to comprise: 1) solvent wash is removed whole organic matters-with tetrachloro-ethylene or similar solvent; 2) alkali cleaning-NH ₄OH+H ₂O ₂+ H ₂O; And 3) acid cleaning-HCl+H ₂O ₂+ H ₂O.Referring to W.Runyan and K.Bean, semiconductor integrated circuit processing technology (1990) here is incorporated herein by reference.Make for semiconductor, such cleaning reagent is bought as packing material usually.But this just means in the factory of manufacturer and makes land used carry out some processing to the solution in these packing materials.As mentioned above, always undesirable to the such processing of ultra-high-purity chemicals.

Other various cleaning chemical methodes have been proposed.For example, it is that the pre-extension of a kind of corrosivity (pre-epitaxy) is cleaned that Shiraki cleans, and it has increased the nitric acid step in cleaning sequence, use high slightly temperature and concentration.Referring to Ishizaki and Shiraki, " low-temperature surface of silicon cleans and the application in silicon MBE ", 133, electron chemistry association magazine (J.ELECTROCHEM.Soc.) 666 (1986) here is incorporated herein by reference.

RCA acid cleaning solution is generally HCl+H ₂O ₂+ H ₂O, its ratio is 1: 1: 6 or 1: 2: 8.According to one of disclosed innovative content here, RCA acid cleaning solution (or similarly cleaning solution) mixes come in situ preparation by the ultrapure HCl with on-the-spot purifying with the ultrapure hydrogen peroxide of on-the-spot purifying in wafer-fabs.Thereby purity improves, and the risk of nd accidental contamination descends.

The accompanying drawing summary

Description illustrates disclosed invention, and the present invention of these description of drawings is important exemplifies embodiment, therefore incorporates this specification here as a reference into, wherein:

Fig. 1 is the process chart of an embodiment of the ultrapure hydrochloric acid unit of preparation.

Fig. 2 is the calcspar of semiconductor fabrication lines of the purification devices that can comprise Fig. 1.

Fig. 3 is the calcspar that semiconductor cleans workshop section in wafer-fabs, wherein can comprise the hydrochloric acid purifying of Fig. 1.

Description of Preferred Embodiments

To be described (this embodiment only as example of the present invention, and not as restriction of the present invention) to many novelty contents of the application with particular reference to present embodiment preferred, wherein:

The purifying of HCl

According to the present invention, at first extract the HCl steam out from the vapor space of liquid HCl feed reservoir.Extract steam out with this method and be used as the single-stage distillation, allow some solid impurity and high-boiling-point impurity stay in the liquid phase.The feed reservoir can be any traditional feed basin or other is suitable for adorning the reservoir of HCl, and HCl can be anhydrous form or aqueous solution form (preferred anhydrous form).Reservoir can remain under the normal pressure, perhaps improves the flow velocity of HCl by system if desired, also can remain under the pressure that is higher than normal pressure.Reservoir is preferably temperature controlled, with cause temperature be maintained at about 10 to about 50 ℃ of scopes, preferred about 15 to about 35 ℃, most preferably from about 20 to about 25 ℃.

Comprise periodic table I and II family metal by extracting the removable impurity of HCl steam out, and because they contact the impurity of the form complexed that generates with HCl from vapour phase.Also removed the oxide and the carbonate of these metals, and hydride such as beryllium hydride and magnesium hydride; Iii group element and oxide thereof, and the hydride of these elements and halid adduct; Transition metal hydride; And heavy hydrocarbon and halohydrocarbon class such as pump oil.

The HCl that extracts out from reservoir is by filter, to remove any solid matter that steam is carried secretly.Micro-filtration and ultrafiltration apparatus and film are commercially available and be used.The brand of filter and type can be selected as required.Embodiment preferred is used a kind of coarse filter at present, then uses 0.1 micron filter in ion purifier front, and does not have further filtration later at the ion purifier.

Filtered steam is then by scrubber, and steam washs with low pH value pure water (preferred deionized water) there.Low pH value water is preferably the HCl aqueous solution, and it is saturated by the scrubber circulation concentration to be increased to.This scrubber is easy to the scrubbing tower operation as traditional reflux type.Though operating temperature is unimportant, scrubbing tower is preferably operated down at about 10 to about 50 ℃, preferred about 15 to about 35 ℃.Equally, operating pressure is unimportant, although preferably at about normal pressure to being higher than about 30 pounds/inch of atmospheric pressure ²Down operation of pressure.Scrubbing tower is equipped with traditional tower packing usually, makes fully contact between the liquids and gases, and preferably has a mist elimination section.

In a present preferred embodiment, about 3 feet of the packed height of tower (0.9 meter), about 7 inches of internal diameter (18 centimetres), make packing volume reach 0.84 cubic feet (24 liters), and operation at about 0.3 inches of water(in H of pressure drop (0.075 kPa) and under less than 10% liquid flooding, rate of circulating flow is about 2.5 gallon per minute (0.16 liters/second) under its normal condition, and be 5 gallon per minute (0.32 liters/second) under 20% liquid flooding, gas feed is below filler, liquid-inlet is above filler, but below the mist elimination section.For the tower of this explanation, preferred filler is that nominal dimension is less than the eighth filler of tower diameter.The mist elimination section of tower has similar or closeer filler, and conventional structure is arranged in addition.Should be appreciated that explanations all in this section and size all are example.Each system parameter all is variable.

In typical operation, at first use the saturated deionized water of HCl, generate washing medium as beginning.In the scrubber operating process, regularly take out small amount of liquid in the tower still, so that remove the impurity of accumulation.

The example of the impurity of removing with scrubber comprises reactive volatile materials, as metal halide; The halide of phosphorus, arsenic and antimony and hydride; Transition metal halide; And the halide and the hydride of III and VI family metal.

Device as described herein can be by batch (-type), continous way or semi continuous operation.Continous way or semi continuous operation are preferred.The volume processing speed of HCl purification system is unimportant, can change in wide region.But, in the great majority operation that the present invention uses, the flow velocity of HCl by system about 200 milliliters/hour to thousands of liters/hour scope.

Optional is, the HCl that leaves scrubber can be further purified before use, and this particular type that is used for manufacture process wherein with the HCl purifying is relevant.For example, it is favourable dewater unit and distilling apparatus being arranged in the system in some cases.Destilling tower also can be operated by intermittent mode, continuation mode or semicontinuous mode.In intermittently operated, typical operating pressure is 300 pounds/inch ²Absolute pressure (2068 kPas), batch of material amount are 100 pounds (45.4 kilograms).In this example, the diameter of tower is 8 inches (20 centimetres), and tower height is 72 inches (183 centimetres), under 30% liquid flooding, operate, steam velocity is 0.00221 feet per second (0.00067 meter per second), and the height that is equivalent to a theoretical plate is 1.5 inches (3.8 centimetres), 48 theoretical plates.In this example, reboiler (boiler) size is diameter about 18 inches (45.7 centimetres), long 27 inches (68.6 centimetres), reflux ratio 0.5,60 of recirculated cooling water inlet temperatures (15.6 ℃), 90 of outlet temperatures (32.2 ℃).Equally, this is an example, can use at the destilling tower that very wide variation is arranged aspect structure and the operating parameter.

Decide on its purposes, whether no matter have distilation steps, purified HCl all to can be used as the gas or the aqueous solution of purifying, under this latter event, purified HCl is dissolved in (preferred deionized water) in the pure water.The ratio and the method for mixing are conventional.

According to the present invention, the flow chart of describing an example of HCl purification devices is shown in Fig. 1.Liquid HCl is stored in the reservoir 11.Extract HCl steam 12 out from the vapor space of reservoir, then by stop valve 13, filter 14.The flow velocity of filtered HCl steam 15 is controlled with pressure regulator 16, and this steam 15 is sent to the scrubber 17 that packing section 18 and mist elimination filling 19 are housed then.Flow downward through saturated moisture HCl20, and the HCl steam upwards flows, liquid is controlled liquid level with circulating pump 21 circulations with liquid level sensor 22.Extract waste liquid 23 out the regular residual liquid at the bottom of scrubber.Deionized water 24 is sent into scrubber 17, keep high pressure with pump 25.HCl26 through washing is sent to one of three selective flow processs.They are: (1) destilling tower 27, HCl is through being further purified there.The HCl28 through distillation that will obtain then delivers to the use point.(2) dissolver 29, and HCl mixes with deionized water 30 there, obtains aqueous solution 31, and it is delivered to the use point.For there being many places to use factory's operation of point, aqueous solution can be collected in the basin, and HCl therefrom extracts out in each pipeline of many use points of delivering to same factory.(3) feed-line 32, and pipeline 32 is delivered to the use point with gas form HCl.

In these selective flow processs, do not use second flow process of destilling tower 27 and the 3rd flow process to be suitable for producing the HCl of the content of any metal impurities less than 100ppt.But, to use for some, it is preferred that destilling tower 27 is arranged.In this case, destilling tower will be removed the non-condensable gas that may disturb cleaning, as oxygen and nitrogen.In addition, because the HCl that leaves scrubber 17 is by water saturation, as a kind of selection, dewater unit can be added in the system between scrubber 17 and the destilling tower 27, decides on the feature and the efficient of destilling tower.

With regard in these selective flow processs any, the gaseous state HCl or the aqueous solution logistics of generation all can be divided into two or more tributaries, each delivers to different use points, therefore, purification devices is delivered to purified HCl many use points simultaneously.

The experiment brief summary

Two independent HCl steel cylinders that obtained by Matheson Gas Products are used for this research.Notice that the impurity composition in these two steel cylinders has difference, it may reflect the variation in general HCl source.The purpose of this research is to develop the purification process that in fact is used for any charging, rather than optimizes the method that is used for particular batch.

Whole experimental procedure all ventilation arranged and do not control in the vent cabinet of internal ambience and carry out.The floor is undressed concrete, and the result of therefore very possible Ca, K and Na is higher than and obtains in the actual use point system that environment control is arranged.

1/4 inch pipe joint is arranged the sampler of being made by CGA and with the bellows sealed valve of 1/4 inch pipe connections, the both is the stainless steel manufacturing.The outlet of valve is connected with 1/4 inch tetrafluoroethene short tube, so that liquid or steam can directly enter sample bottle.In this way, can directly in sample bottle, prepare moisture HCl sample, and not need liquid in unsteered environment, to shift.

Before adding about 100 milliliters of DI and covering bottle, by making sample bottle 4 times with thorough cleaning of DI and emptying.By advancing among the DI that is added in advance the sample bottle to produce sample from the HCl bubbling that selected source and method obtain.In most of the cases, continue to add HCl, until the solution in the sample bottle is by till saturated, this point can be by being confirmed through solution and the HCl that is discharged in the vent cabinet waste gas.When saturated, feel awfully hot when sample solution is touched with hand, and after the tight also cooling of lid, sample bottle can the part depression.

Simulation ion purifier (" IP ") system is made by 1 inch tetrafluoroethene pipe.One end of connecting leg is welded to the tight part of lid of about 1 foot high pipe.Another part of connecting leg is with on the cap that two 1/4 inch holes are arranged on the cap.1/4 inch tetrafluoroethene pipe is inserted this two friction tight holes, and a pipe reaches the bottom of device downwards, and another root pipe only passes the top.4 inches hypomeres of assembly are equipped with the Raschig ring that is cut into by 1/4 inch thin-walled tetrafluoroethene pipe.In experimentation, the IP of this simulation about 100 milliliters of DI that pack into.HCl gas feeds by the bottom pipe, can obtain the gas/liquid interface.Though this assembly has the IP of packed tower effective like that far away from well-designed, can estimate the IP performance of worst case.The bottom sample of this IP need increase processing, so that bottom sample is transferred in the sample bottle, is used for laboratory experiment.Owing to this reason, because the pollution that environment causes, but IP bottom sample energy measurement De Genggao.

By steel cylinder being inverted and liquid being entered in the pre-prepd shuttle, from each steel cylinder, get the HCl liquid-like.The impurity of measuring is the worst real situation, because this liquid sampling technology usually also makes sample that more particles is arranged, and extra processing can make sample be exposed in the room air for a long time.The ICP result of the liquid that is taken out by two steel cylinders lists table 1 in.These results have normalized to 37.25%HCl, and it is the nominal size that is used the moisture HCl that the some system obtains by HCl.Remarkable excessive the making of Fe and other pollutant do not need sensitive more ICP/MS test; Therefore, the actual content of more unessential pollutant is ignorant.But as long as these impurity can be reduced to acceptable level in product, so accurate content has only technical meaning.Fortunately be that all available distillation of all these impurity and/or IP technology are removed.

Following element is found in one or two steel cylinder of being analyzed: Al, B, Ba, Cr, Cu, Fe, K and Na.Pollution concentration and remove technology and will in the lower part, discuss.

Many experiments have been carried out, so that confirm this purifying basic principle for HCl.For easy and clear for the purpose of, more similar experiments have been described in grouping.

The measurement of liquid anhydrous HCl

Measure anhydrous liquid HCl in the water by directly being absorbed in the steel cylinder inversion and with anhydrous liquid HCl.This represents the worst a kind of situation, because solid impurity also may enter in the solvent.Then sample is sent to the icp analysis that carries out metal.(steel cylinder 1: sample number 062993602, steel cylinder 2: sample number 062993605).

The measurement of the anhydrous HCl of steam

In these experiments, with top exit pipeline support steel cylinder.Anhydrous HCl steam steams from liquid, and is dissolved in a small amount of ultrapure water sample by injection spray pipe.The single-stage distillation that this method representative is traditional.Compare with the purifier experiment with these data.(steel cylinder 1: sample number 071293601, steel cylinder 2: sample number 062993603).

The ion purifier is measured

These laboratory scale experiments were carried out with former described equipment.Ultra-pure water is packed into the simulation purifier and the outlet of purifier received another part ultra-pure water after, slowly the HCl pneumatic transmission is gone into experimental provision.Along with HCl is absorbed into the phase I purifier sizable heat release is arranged, reaching before the boiling point of system, temperature in the purifier and concentration increase.When reaching the boiling point of system, HCl gas no longer is absorbed in the purifier, but passes through the liquid bubbling along the circuitous path that the Raschig ring filler provides.In this way, steam is washed by water-bearing media.There are the metal impurities of bigger affinity to stay in the liquid phase aqueous solution than vapor state.Then, purified gas is absorbed in next stage to form hydrochloric acid.Staying liquid (" bottom " sample) and " through what wash " product sample (" product ") of purifier all sends to then and carries out the analysis of ICP/MS method.Two steel cylinders all respectively are used for several experiments, are listed in the remainder of table 1.

The experiment brief summary

The comparative descriptions of the liquid that each steel cylinder obtains and the steam that steams from this liquid by the simple distillation (steam of the liquid of steel cylinder 1 and steel cylinder 1, the steam of the liquid of steel cylinder 2 and steel cylinder 2) obtainable purifying, and showing that good purifying is arranged, its separation factor is 10-5000.But the content of many species still surpasses 1ppb.Connect distillation ability preface or multistage if increase, though can further improve purity, it significantly increases expense and complexity.But the impurity content of the exported product of purifier has remarkable decline than simple distillation scheme.In addition, for any specific element, the bottom sample of any once experiment is all much higher than product stream, and this has illustrated the separating effect of this technology.Purifier is all much simple as with much economical than the multistage distillation system on making and operating.

Steel cylinder 2IP simulation-I

Experimental work: open the basin valve, do not leak.Open sample valve, a large amount of bubblings and liquid are taken waste liquid out of.Close sample valve, some resorptions are arranged.Reopen with suitable speed.In being injected into DI with discarded HCl gas in former seconds.The DI sample is still transparent, and the IP bottom becomes very yellow.Take out the sample ascending pipe, cover the HClS outturn sample.Take out the sample cell of delivering to IP from sample valve, close sample valve.Pour the IP bottom sample into shuttle.

Sample number: IP bottom 063093501, HClS product 063093502.

Steel cylinder 1IP simulation

Experimental work: open valve and obtain good HCl air flow direction IP.When saturated, HCl gas passes through IP.After reaching the pipeline cleaning several seconds, the product pipeline is introduced sample bottle.After sample is saturated, remove the product pipeline.Observe, the gas vent from valve produces and leaks, and sucks back and wash the hole that must corrode in the bellows sealing too early.From IP basin recovery sample.

Sample number: IP product 071293603, IP bottom sample 071293602

Steel cylinder-2IP test

Experimental work: device and the step identical with former test, but do not have (NH ₄) ₂S.

Sample number: IP bottom sample 071493603, IP product 071493604

The sample analysis table

Below three part tables explanations relate to the result of the test of above-mentioned each sample:

HCl laboratory scale result of the test:

Sample number	????062993602	??062993603	??062993605	??063093601	??063093602
						????Id：	????93-7239	??93-07240	??93-07242	??93-07338	??93-07339
Sample	Steel cylinder 1 liquid	Steel cylinder 2 steams	Steel cylinder 2 liquid	Steel cylinder 2IP	Steel cylinder 2IP
										Bottom sample	Product
Analyze	????6.10	????17.31	????6.80	????34.55	????15.34
						?Ag		????＜2.15
Al	????＜136.18	????16.89	????164.34	????191.91	????＜54.15
						Au		????＜2.15		????＜24.04	????＜54.15
B	????2070.12	????4.41	????745.00	????410.77	????＜27.20
						Ba	????36.64	????＜2.15	????＜12.60	????＜2.48	????＜5.59
Be	????＜1.83	????＜0.65	????＜1.64	????＜0.32	????＜0.73
						Bi	????＜678.44	????＜2.15	????＜608.60	????＜	????＜269.78
Ca	????＜7.33	????＜2.58	????8.44	????＜1.29	????＜
						Cd	????＜14.05	????＜2.15	????＜12.60	????＜	????＜5.59
Co	????＜136.18	????＜2.15	????＜122.16	????＜	????＜54.15

Sample number	????062993602	????062993603	????062993605	????063093601	??063093602
						????Id：	????93-7239	????93-07240	????93-07242	????93-07338	??93-07339
Sample	Steel cylinder 1 liquid	Steel cylinder 2 steams	Steel cylinder 2 liquid	Steel cylinder 2IP	Steel cylinder 2IP
										Bottom sample	Product
Cr	????775.53	????＜24.10	????＜61.35	????27276.06	????＜27.20
						Cu	????1337.34	????2.71	????＜61.35	????354.71	????＜27.20
Fe	????144225	????29.22	????129696	????84865.31	????＜27.20
						Ga	????＜678.44	????＜239.08	????＜608.60		????＜269.78
Ge	????＜678.44	????＜239.08	????＜608.60	????＜119.78
						In		????＜2.15
K	????＜1801.43	????2.39	????3.62
						La		????＜2.15
?Li	????＜14.05	????＜2.15	????＜12.60	????＜2.48	????＜5.59
						Mg	????＜1.83	????＜0.65	????＜1.64	????＜0.32	????＜0.73
Mn	????＜14.05	????＜4.95	????＜12.60	????2043.09	??＜5.59
						Mo	????＜183.20	????2.71	????＜61.35	????414.01	????＜27.20
Na	????293.11	????0.97	????＜0.55	????＜47.98	????＜108.06
						Ni	????＜271.74	????＜95.76	????＜243.77	????14402.97	????＜108.06
P	????＜136.18	????＜47.99	????＜122.16	????＜24.04	????＜54.15
						Pb		????＜2.15
Pd	????＜678.44	????＜2.15	????＜608.60	????＜119.78	????＜269.78
						Pt	????＜678.44	????＜2.15	????＜608.60	????＜119.78	????＜269.78
Sb	????＜678.44	????＜2.15	????＜608.60	????＜119.78	????＜269.78
						Sn	????＜339.52	????＜2.15	????＜304.57	????＜59.95	????＜135.01
Sr	????＜68.39	????＜2.15	????＜61.35	?????＜12.08	????＜27.20

Sample number	????062993602	????062993603	????062993605	????063093601	??063093602
						????Id：	????93-7239	????93-07240	????93-07242	????93-07338	??93-07339
Sample	Steel cylinder 1 liquid	Steel cylinder 2 steams	Steel cylinder 2 liquid	Steel cylinder 2 IP	Steel cylinder 2 IP
										Bottom sample	Product
Ta	????＜678.44	????＜2.15	????＜608.60	????＜119.78
						Ti	????＜136.18	????＜47.99	????＜122.16	????＜24.04	????＜54.15
Tl		????＜2.15
						V	????＜68.39	????＜24.10	????＜61.35	????＜12.08	????＜27.20
W		????＜2.15
						Zn	????＜68.39	????＜24.10	????＜61.35	????152.02	????＜27.20
Zr	????＜189.30	????＜2.15	????＜122.16	????＜24.04	????＜54.15

Sample number	??070193601	??070193602	??071293601
				????Id	??93-07388	??93-07389	??93-07890
Sample	Steel cylinder 2 IP	Steel cylinder 2 IP	Steel cylinder 1 steam
					Bottom sample	Product
Analyze	????33.92	????14.42	????18.49
				Ag	????0.00	????＜2.58	????＜44.93
Al	????＜24.49	????2.40
				Au	????0.00	??＜2.58
B	????＜12.30	????3.93	????＜22.56
				Ba	????＜2.53	????＜2.58	????8.06
Be	????＜0.33	????＜2.58	????＜0.60
				Bi	????＜122.01	????＜2.58	??＜223.82
Ca	????0.00	????＜3.10	????＜2.42

Sample number	070193601	070193602	071293601
				????Id	?93-07388	?93-07389	?93-07890
Sample	Steel cylinder 2 IP	Steel cylinder 2 IP	Steel cylinder 1 steam
					Bottom sample	Product
Cd	????＜2.53	????＜2.58	????＜2.62
				Co	????＜24.49	????＜2.58	????＜44.93
Cr	????＜12.30	????＜2.58	????＜22.56
				Cu	????＜12.30	????＜2.58	????＜22.56
Fe	????124.09	????3.69	????＜22.56
				Ga	????＜122.01	????＜0.00	????＜223.82
Ge	????0.00	????＜0.00	????＜223.82
				In	????0.00	????＜2.58
K	????0.00	????7.17
				La	????0.00	????＜2.58
Li	????＜2.53	????＜2.58	????＜4.63
				Mg	????＜0.33	????＜2.58	????＜0.60
Mn	????91.15	????0.00	????＜4.63
				Mo	????＜12.30	????＜2.58	????＜22.56
Na	????＜48.87	????11.47	????＜89.65
				Ni	????＜48.87	????0.00	????＜89.65
P	????＜24.49	????0.00	????＜44.93
				Pb	????0.00	????＜2.58
Pd	????＜122.01	????＜2.58	????＜223.82
				Pt	????＜122.01	????＜2.58	????＜223.82
Sb	????＜122.01	????＜2.58	????＜223.82

Sample number	??070193601	??070193602	??071293601
				????Id	??93-07388	??93-07389	??93-07890
Sample	Steel cylinder 2 IP	Steel cylinder 2 IP	Steel cylinder 1 steam
					Bottom sample	Product
Sn	??＜61.06	??＜2.58	??＜112.01
				Sr	??＜12.30	??＜2.58	??＜22.56
Ta	????0.00	??＜2.58	??＜223.82
				Ti	??＜24.49	????0.00	??＜44.93
Tl	????0.00	??＜2.58
				V	??＜12.30	????0.00	??＜22.56
W	????0.00	??＜2.58
				Zn	??＜12.30	????0.00	??＜22.56
Zr	??＜24.49	??＜2.58	??＜44.93

Sample number	????071293602	????071293603	????071493603	????071493604
					????Id	????93-07891	????93-07892	????93-07974	????93-07975
Sample	Steel cylinder 1 IP	Steel cylinder 1 IP	Steel cylinder 1 IP	Steel cylinder 1 IP
						Bottom sample	Product	Bottom sample	Product
Analyze	????33.33	????16.67	????35.08	????14.49
					Ag	????＜24.92	????＜49.83	????7.33	????＜2.57
A1	????0.00	????0.00	????3.57	????0.67
					Au	????0.00	????0.00	????＜1.06	????＜2.57
B	????＜12.52	????＜25.03	????19.64	????＜2.57
					Ba	????5.59	????＜5.14	????＜1.06	????＜2.57
Be	????＜0.34	????＜0.67	????＜1.06	????＜2.57
					Bi	????＜124.17	????＜248.26	????＜1.06	????＜2.57
Ca	????＜1.34	????＜2.68	????19.76	?????1.90
					Cd	????＜1.45	????＜2.90	????＜1.06	????＜2.57
Co	????＜24.92	????＜49.83	????2.34	????＜2.57
					Cr	????＜12.52	????＜25.03	????0.00	????0?00
Cu	????＜12.52	????＜25.03	????21.02	????＜2.57
					Fe	????62.59	????＜25.03	????0.00	????1.75
Ga	????＜124.17	????＜248.26	????0.00	????0.00
					Ge	????＜124.17	????＜248.26	????0.00	????0.00
In	????0.00	????0.00	????＜1.06	????＜2.57
					K	????0.00	????0.00	????0.00	????2.08
La	????0.00	????0.00	????＜1.06	????＜2.57
					Li	????＜2.57	????＜5.14	????＜1.06	????＜2.57
Mg	????＜0.34	????＜0.67	????11.79	????＜2.57

Sample number	????071293602	????071293603	????071493603	????071493604
					????Id	????93-07891	????93-07892	????93-07974	????93-07975
Sample	Steel cylinder 1 IP	Steel cylinder 1 IP	Steel cylinder 1 IP	Steel cylinder 1 IP
						Bottom sample	Product	Bottom sample	Product
Mn	????＜2.57	????＜5.14	????0.00	????0.00
					Mo	????＜12.52	????＜25.03	????29.63	????＜2.57
Na	????＜49.73	????＜99.44	????1.71	????4.19
					Ni	????＜49.73	????＜99.44	????0.00	????0.00
P	????＜24.92	????＜49.83	????0.00	????0.00
					Pb	????0.00	????0.00	????＜1.06	????＜2.57
Pd	????＜124.17	????＜248.26	????＜1.06	????＜2.57
					Pt	????＜124.17	????＜248.26	????＜1.06	????＜2.57
Sb	????＜124.17	????＜248.26	????＜1.06	????＜2.57
					Sn	????＜62.14	????＜124.24	????＜1.06	????＜2.57
Sr	????＜12.52	????＜25.03	????＜1.06	????＜2.57
					Ta	????＜124.17	????＜248.26	????＜1.06	????＜2.57
Ti	????＜24.92	????＜49.83	????0.00	????0.00
					Tl	????0.00	????0.00	????＜1.06	????＜2.57
V	????＜12.52	????＜25.03	????0.00	????0.00
					W	????0.00	????0.00	????＜1.06	????＜2.57
Zn	????40.23	????＜25.03	????0.00	????0.00
					Zr	????＜24.92	????＜49.83	????＜1.06	????＜2.57

Improve and work-around solution

Recognize that as those skilled in the art disclosed in this application novelty basic principle can improve and change in very big range of application, therefore scope required for protection is not subjected to the restriction of given concrete illustrative disclosure.

For example, disclosed innovative technology is not strictly limited to the manufacturing of integrated circuit, also can be used for making discrete semiconductor element, as optoelectronic device and power set.

As another example, disclosed innovative technology also can be used for having adopted other technology manufacturing of method for manufacturing integrated circuit, as film magnetic head and active matrix LCD; But main application is in the integrated circuit manufacturing, and the application of disclosed technology in other field is less important.

As another example, be not strict with and use scrubber to carry out liquid-gas contact; Available bubble tower (bubbler) replaces scrubber, though because the gas/liquid contacting efficiency of bubble tower is lower, this replacement is not too wished.

Optional is, the use that can combine with disclosed purifier apparatus of other filtration or fillter section.

Should also be noted that if necessary, but additive is added in the purified water, though do not doing like this in the embodiment preferred at present.

As above-mentioned, main embodiment is on-the-spot purification system.On the other hand, in a less preferred class embodiment, disclosed purification system is also applicable to the part as the manufacturing installation of producing the ultra-high-purity chemicals that supplies shipment; But this alternative embodiment can not obtain the advantage of on-the-spot purifying as discussed above.So intrinsic risk that application ran into is the handling problem of ultra-high-purity chemicals as discussed above; But for user's (having the processing of following) of needs packings chemicals, disclosed innovative technology is higher than the accessible initial purity of other technology an approach is provided for reaching.In addition, in such application, also can use dryer section later at the ion purifier.

As mentioned above, main embodiment relates to providing semiconductor is made the most important ultrapure water chemistries that contains.But the gas that disclosed system and method embodiment also can be used for providing purified flows.(in many cases, using drier to be suitable in the purifier downstream).

Should also be noted that ultrapure chemicals piping can comprise online or reservoir with pressure in semiconductor making apparatus in early stage.Therefore " directly " pipe in the claims send not get rid of and uses such reservoir, but they can not be exposed in the uncontrolled atmosphere.

Claims (38)

1. on-the-spot assistant system that the superhigh-purity reagent that contains HCl is provided for the semiconductor manufacturing operation in semiconductor equipment manufacturing works, this system comprises: one is connected to liquid HCl source and provides the source vaporize of HCl steam flow by it; Described HCl steam flow is connected to pass through the ion purification devices, and it makes the high purity water circular flow that contains concentrated hydrochloric acid contact with described HCl steam flow; And the preparation facilities of a connection, it receives the described HCl steam flow from described purification devices, and makes described HCl steam and liquid, aqueous merging, makes the ultrapure aqueous solution that contains HCl; And a piping, it delivers to respectively using a little of semiconductor equipment manufacturing works with described aqueous solution.

2. according to the system of claim 1, wherein between described source vaporize and described purification devices, also has particulate filter.

3. according to the system of claim 1, wherein said liquid HCl is made up of anhydrous HCl in the source.

4. according to the system of claim 1, wherein said circulation high purity water does not contain any additives.

5. according to the system of claim 1, wherein said liquid HCl has only normal business level purity in the source.

6. according to the system of claim 1, wherein said vaporizer is a big basin.

7. according to the system of claim 1, wherein said vaporizer is operated under controlled temperature, and it is connected to receive the liquid HCl of arrogant basin.

8. on-the-spot assistant system that the superhigh-purity reagent that contains HCl is provided for the semiconductor manufacturing operation in semiconductor equipment manufacturing works, this system comprises: one is connected to receive liquid HCl and to provide the source vaporize of HCl steam flow by it; Described HCl steam flow is connected to pass through the ion purification devices, and it makes the high purity water circular flow that contains concentrated hydrochloric acid contact with described HCl steam flow; And the preparation facilities of a connection, it receives the described HCl steam flow from described purification devices, and makes described HCl steam and liquid, aqueous merging, makes the ultrapure aqueous solution that contains HCl; Thereby described ultrapure aqueous solution can use in semiconductor equipment manufacturing works, and does not need to carry in a large number or liquid surface is exposed in any environment.

9. system according to Claim 8 wherein is provided with particulate filter between described source vaporize and described purification devices.

10. system according to Claim 8, wherein said liquid HCl is made up of anhydrous HCl in the source.

11. system according to Claim 8, the high-purity current of wherein said circulation do not contain any additives.

12. system according to Claim 8, wherein said liquid HCl has only normal business level purity in the source.

13. system according to Claim 8, wherein said vaporizer are big basin.

14. system according to Claim 8, wherein said vaporizer is operated under controlled temperature, and is connected to receive the liquid HCl of arrogant basin.

15. the on-the-spot assistant system that ultra-pure HCl is provided for the semiconductor manufacturing operation in described factory in semiconductor equipment manufacturing works, this system comprises: one is connected to receive liquid HCl and to provide the source vaporize of HCl steam flow by it; Described HCl steam flow is connected to pass through the ion purification devices, it makes the high-purity water circular flow that contains concentrated hydrochloric acid contact with described HCl steam flow, and the drier device of a connection, it receives the described HCl steam flow from described purifier, and dry described HCl steam; And a piping, it delivers to respectively using a little of semiconductor equipment manufacturing works with described aqueous solution.

16., wherein between described source vaporize and described purification devices, be provided with particulate filter according to the system of claim 15.

17. according to the system of claim 15, wherein said liquid HCl is made up of anhydrous HCl in the source.

18. according to the system of claim 15, wherein said high purity water circular flow does not contain any additives.

19. according to the system of claim 15, wherein said liquid HCl has only normal business level purity in the source.

20. according to the system of claim 15, wherein said vaporizer is big basin.

21. according to the system of claim 15, wherein said vaporizer is operated under controlled temperature, and is connected to receive the liquid HCl of arrogant basin.

22. a system for preparing ultra-pure HCl, described system comprises:

(a) reservoir that the liquid HCl of vapor space is arranged on storage liquid;

(b) extract the connecting line that contains the HCl steam out from described vapor space;

(c) from the steam of extraction like this, remove the particulate filtration film; And

(d) liquid-vapor interface contact chamber, the steam that filters by described filter membrane contact with the HCl aqueous solution in deionized water therein, is the HCl gas of purifying through the steam that washs like this.

23. according to the system of claim 22, wherein also comprise a destilling tower, be used to distill steam from described scrubber.

24. a system of making high-accuracy electronic component, described system comprises:

(a) one contains the production line that carries out the work station of various steps on many wafers that are used for containing semi-conducting material in the electronic component manufacturing, and at least one uses gaseous state HCl as the gas source of handling described workpiece in the described work station;

(b) the purifying servicing unit that links to each other with described work station by pipeline, so that the HCl of described ultra-high purity form to be provided, described servicing unit comprises:

(i) liquid HCl reservoir that vapor space is arranged above storage liquid HCl;

(ii) extract the connecting line that contains the HCl steam out from described vapor space for one;

(iii) from the steam of extraction like this, remove the particulate filtration film for one; And

(iv) a scrubber is used for making the steam that filters by described filter membrane to contact at the aqueous solution of deionized water with HCl, and so the steam of washing is the HCl gas of purifying;

(c) described purification devices links to each other with described work station by pipeline, so that the HCl of described ultra-high purity form to be provided.

25. according to the system of claim 24, wherein said servicing unit also comprises the destilling tower that is used to distill from the steam of described scrubber.

26. according to the system of claim 24, wherein said servicing unit also comprises described purified HCl gas and purified water is merged to make the equipment of the HCl aqueous solution.

27., wherein leave described servicing unit in the place that is positioned within about 30 centimetres of described equipment, so that the product of step (b) is directly used in described workpiece with the HCl of described servicing unit purifying according to the system of claim 24.

28. according to the system of claim 24, the size of wherein said servicing unit can be produced described purified HCl gas to about 200 liters/hour speed with about 2.

29. according to the system of claim 24, (ii), the (iii) and (iv) part of wherein arranging described servicing unit is to be used for continuous or semicontinuous stream.

30. one kind for the work station of making in the high-accuracy electronic element production line provides high-purity HCl compositions and methods, described method comprises:

(a) from the reservoir that contains HCl, extract HCl gas out in the vapor space of liquid HCl top;

(b) make described HCl gas by filter membrane, therefrom to remove particle greater than 0.005 micron;

(c) make described HCl gas pass through scrubber, thereby described HCl gas is contacted with the aqueous solution of HCl in deionized water through filtration like this; And

(d) retrieve described HCl gas, and described HCl gas is delivered to described work station from described scrubber.

31. according to the method for claim 30, wherein also be included in described HCl gas delivered to before the described work station, will be dissolved in the purified water from the described HCl gas of described scrubber.

32. according to the method for claim 30, wherein also be included in described HCl gas delivered to before the described work station, with described HCl gas by destilling tower so that be further purified.

33. method according to claim 30, wherein also comprise another step: (b ') delivering to described HCl gas before the described work station, will be from the described HCl gas of described scrubber by destilling tower so that be further purified, and will be dissolved in the pure water from the described HCl gas of described destilling tower.

34. according to the method for claim 30, wherein step (b) is carried out to about 50 ℃ temperature range about 10.

35. according to the method for claim 30, wherein step (b) is carried out to about 35 ℃ temperature range about 15.

36. according to the method for claim 33, wherein step (b) and (b ') carry out to about 35 ℃ temperature range about 15.

37. according to the method for claim 30, wherein step (b) about 15 to about 35 ℃ temperature range and at about normal pressure to being higher than about 30 pounds/inch of atmospheric pressure ²Pressure under carry out.

38. according to the method for claim 33, wherein step (b) and (b ') about 15 to about 35 ℃ temperature range and at about normal pressure to being higher than about 30 pounds/inch of atmospheric pressure ²Pressure under carry out.

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