CN1981242A - Ultraviolet-transparent alkanes and processes using same in vacuum and deep ultraviolet applications - Google Patents

Abstract

The present invention is drawn to the use of alkanes that are highly transparent to UV wavelengths ranging from about 170 nm to 260 nm in optical couplants, optical cements, optical elements, optical inspection media for semiconductor wafers and devices, and immersion photolithography, particularly at 193 and 248 nm exposure wavelength.

Description

The alkane of UV transparent is used with the method for using them in a vacuum and deep ultraviolet

Technical field of the present invention

The present invention relates at semiconductor wafer and device, and in the optical coupled agent of immersion lithography process, optical cement, optical element, optical detection medium, be transparent alkane in ultraviolet waves is about the 170-260nm scope, especially 193 and the 248nm illumination wavelength be transparent alkane.These alkanes are useful in vacuum and deep ultraviolet application, wish that wherein the transparency of low wavelength UV radiation increases to some extent.

Background technology of the present invention

Many progress of electronics industry come from the reduction circuit size.Under very short optical wavelength, implement photoetching process and can very directly realize this point.Adopt the method for 193 nanometers (nm) light experiencing commercialization, and adopt the method for 157nm wavelength light to be in the development as next-generation technology.

(people such as Switkes, " J.Vac.Sci.Technol.B ", 19 (6), 2353-6 page or leaf, 11/12 month, calendar year 2001) is immersed in light source and target surface in the high transparent high refractive index liquid in immersion lithography process., pointed in May, the 2003 4ff page or leaf as people such as Switkes at " the micro-lithography method world " (Microlithography World), when using the high index of refraction conductive medium, under certain lambda1-wavelength, can make photoetching process reach higher resolution.Realize the profit potential of this technology, depend on that discriminating has the high refractive index liquid of high transparent and outstanding photochemical stability in VUV/DUV.

All known organic materials absorb the 193nm UV radiation to a certain extent.Whether its problem is can find actual is enough transparent liquid.For example as people such as B.A.Lombos, " chemical physics wall bulletin " (Chemical Physics Letters), 1,42 (1967); People such as G.Belanger, " chemical physics wall bulletin ", 3 (8) and people such as K.Seki, " Acta Physica Sinica " (Phys.Scripta), 41,167 (1990) is disclosed, short chain alkane H (CH ₂) _nH and short chain fluorocarbon F (CF ₂) _nF compares with its long-chain congener, all is transparent relatively at 193nm.

Although know that fluoridizing class is transparent for the UV radiation of some useful wavelength, fluorination may reduce absorptivity, and fluorinated molecule may have low refractive index, and is for example about 1.3, and this is nonconforming for low immersion lithography process at 193nm.

Gaseous matter can be a highly transparent, and its refractive index may be lower than the refractive index of hope.Similarly, the refractive index of low-boiling point liquid also may be low nonconforming, and need the working pressure container to preserve.

Crews, P.; Rodriguez, J.; Jaspars, M., " organic structural analysis " (OrganicStructure Analysis), the Oxford University Press publishes, 1998; The 353rd page discloses 200nm is that cutting back transparent in cyclohexane ends wavelength.

Brief description of the present invention

The invention provides a kind of liquid alkane, wherein oxygen concentration is less than 2ppm, at 193nm wavelength absorption rate≤1cm ^-1

The present invention also provides a kind of method, the light source that provides transmitted wave to be about the UV radiation of 170-260nm is provided this method, and the target surface is provided, irradiation at least a portion target surface, UV radiation from light source along light path is arranged, and at least a portion light path, place the thethea liquid alkane.This liquid alkane is made up of the non-annularity alkane or the ring-type alkane that can be side chain or non-side chain basically.This liquid alkane can contain potpourri and its any combination of the alkane of ring-type and acyclic, side chain and non-side chain.

The present invention also provides a kind of equipment, it comprises that transmitted wave is about the light source of the light of 170-260nm, surface of handling like this, so that when this light source activates, rayed at least a portion surface by this light emitted, and liquid alkane so places between this light source and this surface, so that shines this surperficial at least a portion emission light and propagate by its liquid alkane.This liquid alkane is made up of the non-annularity or the ring-type alkane of side chain or non-side chain basically.This liquid alkane can contain ring-type and acyclic, side chain and the alkane of non-side chain and their combination.

Brief description of drawings

Fig. 1 is the synoptic diagram of Harrick DLC fluid sample unit, demonstrates circular gasket (Spacer), window and associated components.

Fig. 2 shows the minimum deflection ratio juris of using prism unit to measure the liquid refracting index.

Fig. 3 shows the index unit that is installed on the support that uses in the VASE  spectrophotometer.

Fig. 4 has described submergence contact lithograph method equipment.

Fig. 5 has described submergence contact lithograph method optical device.

Fig. 6 shows the wafer exposure platform of submergence contact lithograph method.

Fig. 7 shows with the reciprocal centimetre to be that the decane absorptivity of unit is the wavelength X (1) of unit with the nanometer to sample, and a) primary sample is b) with silica gel treatment.

Fig. 8 shows with the reciprocal centimetre to be that the cyclohexane absorptivity of unit is the wavelength X of unit with the nanometer to sample, a) primary sample, and b) (dotted line and the dotted line) handled with the 3A molecular sieve is c) with silica gel treatment.

Fig. 9 shows that the refractive index of absolute unit of cyclohexane is to being the wavelength X of unit with the nanometer.

Figure 10 demonstration is that the cyclopentane absorptivity of unit is the wavelength X of unit with the nanometer to sample with the reciprocal centimetre, a) primary sample, b) (dotted line and the dotted line) of usefulness 3A molecular sieve processing, c) (solid line) of usefulness silica gel treatment.

The refractive index that Figure 11 shows the cyclopentane absolute unit is to being the wavelength X of unit with the nanometer.

Figure 12 shows that the primary sample cyclohexane is used as immersion liquid, makes the photo of photoresist image.

Figure 13 shows that low absorptivity cyclohexane of the present invention is used as immersion liquid, makes the photo of photoresist image.

Figure 14 shows that the primary sample decahydronaphthalenes is used as immersion liquid, makes the photo of photoresist image.

Figure 15 shows that decahydronaphthalenes of the present invention is used as immersion liquid, makes the photo of photoresist image.

Figure 16 demonstration does not use immersion liquid to make the photo of photoresist image.

Figure 17 shows the specific embodiments that is suitable for implementing the circulation system of the present invention.

Describe in detail

The present inventor finds, basically by the liquid alkane of non-annularity and/or ring-type alkane, side chain and/or non-side chain alkane or its compositions of mixtures, at about 170-260nm (VUV-VUV), especially 193 and the wave-length coverage of 248nm in imaging applications in, and in other application of the high transparent condensed phase optical modules of needs (such as optical adhesive composition, film polymer solvent, index-matched liquid etc.), demonstrate astoundingly high applicability. What wherein pay special attention to is, at the 193nm exposure wavelength, their applicability in the new appearance district of immersion lithography process, wherein in photoetching process equipment, in the photoetching process equipment that for example in the microcircuit manufacturing technology, extensively adopts, its target surface portion ground or be immersed in fully high transparent and refractive index and be higher than in the liquid of air or other atmosphere at least. Preferably, all this target of submergence is surperficial.

Preferably, this liquid alkane basically by non-annularity or ring-type, side chain or non-side chain alkane or its compositions of mixtures. The transparency of these liquid alkanes and high photochemical stability when the immersion lithography process in VUV/deep ultraviolet (VUV/DUV) district that is used for electromagnetic spectrum, provide extra high applicability.

Term used herein " imaging ", " imaging applications ", " the one-tenth image " refer to adopt the photoactivation method to form image at base material, this photoactivation method comprises provides wavelength about 170-260nm, the light source of about 193-248nm preferably, utilizing emitted light irradiation at least a portion surface, and liquid alkane so is placed between light source and the surface, to cause this surperficial at least a portion utilizing emitted light transmission of irradiation by liquid, wherein this liquid is basically by non-annularity or ring-type alkane or its compositions of mixtures of side chain or non-side chain. Without any restriction, this image can comprise and covers surface and/or crested surface fully fully for the shape of the image that forms. Term " light " and " radiation " are used interchangeably in this article, mean the nanometer at wave-length coverage 170-260, very especially 193 and 248nm in non-ionized electromagnetic radiation, do not plan to comprise ionising radiation.

Unless otherwise noted, the concentration of representing with parts per million (ppm) (ppm) herein means with described composition total weight to be parts per million (ppm) by weight of base.

During herein with scope, preferable range or a series of upward preferred value or following preferred value mode description amount, concentration or other values or parameter, amount, concentration or other values of describing or parameter need comprise the gamut that is formed by any a pair of any higher limit or preferred value and any a pair of any lower limit or preferred value, and no matter whether these scopes separately disclose.When enumerating numerical range in this article, unless otherwise noted, this scope need comprise its end points, and all integers and mark in this scope.Do not plan when limited range, scope of the present invention just is limited to the particular value of enumerating.

This paper has adopted term " middle distillate " with reference to fractionation, means that the temperature of condensation product reaches that part of condensation product of collecting when stablizing.

Term used herein " it is minimum to contain oxygen " means wherein liquid alkane processing and the atmosphere of preserving.Term used herein " it is minimum to contain oxygen " expression takes steps to reduce the aerial oxygen pollution of liquid alkane.Wish that liquid alkane does not wherein have oxygen when storing, because slow oxidation may be created in the chromophore that 193nm absorbs.And, wish that liquid alkane does not wherein have oxygen when exposure, because the luminous energy of 193nm and oxygen interact, produce ozone.

Term alkane used herein means basically the liquid of being made up of the non-annularity of side chain or non-side chain or ring-type alkane or their any potpourri or composition.Suitable ring-type alkane can contain one or more bigger rings that side chain or unbranched cyclo-butane or any size are arranged, and can be able to interconnect by any way, comprising straight chain, condense, dicyclo, encircle and volution is arranged more.

When alkane has intrinsic high index of refraction again when existing high photochemical stability, be highly transparent under VUV, they are suitable as the immersion liquid in the immersion lithography process very much.Preferred liquid alkane is 0.01-1cm in the absorptivity of 193nm ^-1, oxygen concentration＜2ppm.Preferred alkane comprises cyclopentane, cyclohexane, cycloheptane, cyclooctane, decane, decahydronaphthalenes racemic compound, cis-decahydronaphthalenes, trans-decahydronaphthalenes, outer (exo)-tetrahydro-dicyclopentadiene, 1,1 '-bis cyclohexane, 2-ethyl norcamphane, n-octyl group-cyclohexane, dodecane, the tetradecane, hexadecane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, octahydro indenes and composition thereof.

Preferred alkane is 0.01-0.5cm in the absorptivity of 193nm ^-1, oxygen concentration＜2ppm.Preferred alkane includes but not limited to cyclopentane, cyclohexane, cycloheptane, cyclooctane, n-decane, decahydronaphthalenes racemic compound, cis-decahydronaphthalenes, trans-decahydronaphthalenes, outer-tetrahydro-dicyclopentadiene, 1,1 '-bis cyclohexane, 2-ethyl norcamphane, n-dodecane, the n-tetradecane, n-hexadecane, 2-methyl-pentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, octahydro indenes and composition thereof.

Most preferred alkane be cyclopentane, cyclohexane, decahydronaphthalenes racemic compound, cis-decahydronaphthalenes, trans-decahydronaphthalenes, outer-tetrahydro-dicyclopentadiene, 1,1 '-bis cyclohexane and composition thereof.

The present invention also provides a kind of method, this method comprises provides transmitted wave to be about the light source of 170-260nm UV radiation, the target surface is provided, and UV radiation is along from the light path of light source irradiation at least a portion target surface, and places the thethea liquid alkane at least a portion light path.This liquid alkane is made up of the non-annularity of side chain or non-side chain or ring-type alkane basically.This liquid alkane can contain ring-type and acyclic, side chain and the alkane of non-side chain and any combination thereof.

In some preferred specific embodiments, light source sends 193 or 248nm light.More preferably, this light source is a laser.In some specific embodiments very preferably, this light source is an ArF excimer laser of sending 193nm light.Other suitable light sources include but not limited to lamp, for example deuterium, xenon or halide gas discharge lamp, laser plasma light source, and frequency shift laser, for example double-frequency laser light source or frequency tripled laser light source.

Preferably, this surface is the photoresist surface.More preferably, the photoresist surface is positioned on the silicon wafer.More preferably, illumination is the one-tenth image exposure on preferred photoresist surface.Most preferably, the photoresist surface is immersed in the liquid alkane.Those skilled in the art it will be appreciated that liquid alkane is generally considered to be many organic " good solvent ".In some cases, depend primarily on concrete selection photoresist or other surfacings, this resist may be partially or completely dissolved or swelling or be subjected to other infringements, and reduce the transparency of liquid alkane.Under such certain situation, the external coating of this resist-coating protectiveness in the past.This external coating preferably optics is uniform, to 193 and 248nm only transparent, be attached on this resist, be insoluble in the immersion fluid, and in the process of immersion lithography process, deposit easily, also remove easily subsequently, in the resist that does not have damage, stay bottom resist and sub-image (it be present in the exposure back and in the resist before development of photoresist).

Suitable external coating comprises highly fluorinated polymeric, and they dissolve in the high fluorated solvent.High fluorated solvent is the key factor of preparation external coating method, because they can not influence most photo-corrosion-resisting agent composition.Suitable external coating polymkeric substance comprises perfluorobuttene base vinethene { 1,1,2,3,3,4,4-seven fluoro-4-[(trifluoro vinyls) oxygen]-the 1-butylene } homopolymer, or the amorphous solvable multipolymer of two or more monomers, monomer whose for example be tetrafluoroethene (TFE), hexafluoropropylene (HFP), perfluor dimethyl dioxole [4,5-two fluoro-2, two (trifluoromethyl)-1 of 2-, the 3-dioxole], and perfluoroalkyl vinyl ether, for example perfluorinated methyl ethylene ether and perfluoro propyl vinethene.The multipolymer of enumerating also can contain a spot of termonomers, comprising vinylidene fluoride, fluorothene, trifluoro-ethylene, 3,3,3-trifluoro propene, 3,3,3,2-tetrafluoeopropene, hexafluoro-isobutene [3,3,3-three fluoro-2-(trifluoromethyl) propylene], but these very not many monomers, its polymkeric substance no longer is dissolved in the desired high fluorated solvent.Preferred fluorated solvent comprises Fluorinert ^TMFC-75, Fluorinert ^TMFC-40, Performance Fluid ^TMPF-5080, perfluoro butyl tetrahydrofuran, perfluor tri-butylamine, PFO, perfluoroalkane and perfluor decahydronaphthalenes.Preferred external coating polymkeric substance is Teflon ^TMAF, by DuPont company, WilmingtonDelaware obtains, Cytop ^TMTetrafluoroethene) and poly-(perfluor dimethyl dioxole: the perfluoro propyl vinethene), 40-60: 60: 40 poly-(hexafluoropropylenes:.

In order to prepare this liquid alkane, handle high purity liquid alkane commodity, be no more than 2/1000000ths (weight) (ppm) to guarantee oxygen concentration.In addition, the former state liquid alkane is removed micro quantity organic pollutant through handling.Liquid alkane through processing like this is 0.01-1.cm in the absorptivity of 193nm ^-1In the most preferred specific embodiments of the present invention, the oxygen concentration of liquid alkane after processing is no more than 1ppm.And in specific embodiments very preferably, liquid alkane of the present invention is 0.01-0.5cm in the absorptivity of 193nm ^-1E ₀(removing dosage) and E ₁(exposure dose) is the quality factor that integrated circuit industry adopts.The utmost point low absorptivity of liquid alkane changes into desirable low E ₀And E ₁Level, and they change at fixed laser and can flow down higher throughput rate.In this sense, lower optical absorptivity reduces the photoetching process cost, and the high index of refraction of liquid alkane allows further to reduce the feature dimension of printing simultaneously.Term " E ₀" to remove dosage be a term in this technology, it means outdoor incident light energy exposure, at this moment photoresist can be removed fully behind exposure and then water base developing.Term " E ₁" exposure dose is a term in this technology, it means the exposure of incident light energy, at this moment behind exposure and then water base developing, photoresist can be hopeful the pie graph pattern characteristics of size, as being produced by photomask pattern.

Can buy high-purity (more than 99.9% or 99.9%) cyclohexane and cyclopentane.The high-purity cyclohexane sold of Fluka for example.Before the present invention, in the immersion lithography process of 193nm exposure wavelength, do not think over and used even high-purity these materials of commerical grade, because promptly enable to obtain high-purity cyclohexane, but absorptivity is high too.

The inventor finds that commercially available high-purity alkane can obviously reduce the absorptivity of its VUV by further processing.The degree that the further processing of primary sample must reach depends on the degree of having removed absorption impurity from commercial source.What this paper summarized is the method for purification of liquid alkane, has found that these methods are very useful when preparation is used for the liquid alkane of the open method of this paper.Should understand as those skilled in the art, not all these purification process all are essential under any situation.

In the alkane of commercial source, have some organic impurities, for example aromatic ring, alkene, substituted ring alkane, side chain chain alkoxylation products are as superoxide and ketone etc.Other organic impurities of the absorptance of some organic impurities is the high a plurality of orders of magnitude of cyclo-butane for example.So the alkane that is polluted by 1% or 2% cyclo-butane for example although vapour pressure height and refractive index is low is very transparent, therefore still is applicable to method disclosed herein.On the other hand, the concentration of higher absorption pollutant (for example alkene and carbonyl) is about 1ppm or below the 1ppm, and this is desirable.

Adopt such certain methods, for example fractionation, injection, freezing fusing circulation, zone purification, use as the disposal route of the adsorbent of molecular sieve, carbon, silica gel, aluminium oxide or its potpourri in silicon dioxide, various apertures and so on, can remove high absorption pollutant.

Preferably, this liquid alkane is 0.01-1cm in the absorptivity of 193nm ^-1, 0.01-0.5cm more preferably ^-1Those skilled in the art it should be understood that absorptivity without any lower limit, and it is preferably low as far as possible, as long as oxygen concentration is low satisfactorily.In the present invention's specific embodiments very preferably, liquid alkane is 0.01-0.5cm in the absorptivity of 193nm ^-1Those skilled in the art it should be understood that when obtaining the needed purity of this result, and the sensitive method of measuring pollutant is a spectral absorption method itself.In other words, conclude that the best method of removing maximum impurity is to measure absorptivity.Be lower than 1cm ^-1Absorptivity be the most responsive trace absorbing agent purity indicator that can adopt at present.The absorptivity that reaches among the present invention than knew in the past more than low about 90% or 90%.Therefore, term " absorptivity " means two relevant phenomenons.On the one hand, term " absorptivity " means in method disclosed herein the true absorptivity of the actual liquid alkane that uses, and it may be subjected to externalities, the solubleness of photoresist in liquid alkane of being discussed as this paper front.On the other hand, " absorptivity " also means and adopt the absolute absorption rate of analyzing the spectrographic determination liquid alkane under laboratory condition.The latter is the very desirable method that assessment treats to pollute in the test(ing) liquid alkane absorbent concentration.

People have found that when enforcement is of the present invention silica gel is the very effective adsorbent of very a small amount of organic contaminant in the liquid alkane.People observe, and during with silica gel treatment primary sample alkane, transparency obtains very big improvement.

In some specific embodiments, if especially goods providers is not so done, can worthwhilely be at first to allow the primary sample alkane in no grease distilling apparatus that may be the cleanest, carry out fractionation, the purity of this primary sample alkane is usually greater than 99%.The distillate middle distillate that so obtains mixes with adsorbent mixtures with liquid state again, and this adsorbent mixtures can comprise for example silica gel, 3A and 5A zeolite molecular sieve, aluminium oxide or activated charcoal.Then, the alkane of purifying preferably in inert gas atmosphere, most preferably carries out all subsequent treatment in helium or blanket of nitrogen in containing the minimum atmosphere of oxygen like this.This is included in the immersion lithography process and uses it, and this method is preferably carried out in containing the minimum atmosphere of oxygen.

If silica gel and zeolite adsorbents activate, preferably when cleaning, carry out heat-activated with dry gas stream, then they are the most effective.It is preferred using immediately after adsorbent activates.Under pure air, nitrogen or the helium flow of drying, can realize activation in several hours about 200-500 ℃ of heating.The advantage of 500 ℃ of air is the most of residual organic contaminants that burn in the adsorbent (as silica gel or zeolite).This system cools is during to room temperature to 100 ℃, and this air-flow can be constant.In a selectable mode, stop its air-flow, the blockade system.In another selectable mode, when adsorbent cool to room temperature to 100 ℃, air-flow stops, system pump down.When this adsorbent was in 500 ℃, the benefit that stops air-flow was along with adsorbent cools, to make so and reduced to minimum by any foreign impurity pollution in the gas.

The method for optimizing of a kind of activated silica gel and zeolite adsorbents is as follows.Load adsorbent toward the pipe of the Hastelloy  in clamshell furnace, heated 2 hours down in 500 ℃ at airflow then.Stop airflow, seal Hastelloy pipe two ends immediately.In case the Hastelloy  of sealing pipe cool to room temperature is just transferred to N with it ₂Bag glove is opened this pipe here, and adsorbent is added in the bottle that alkane liquid to be purified is housed.Although adsorbent can unrestrictedly change with the ratio of liquid, found that the adsorbent of 1 volume of liquid use of every 1-20 volume is gratifying.The quantity of sorbent of actual needs will depend on the level of pollutant in the primary sample liquid.Therefore, have reason the maximum efficiency that suggestion adopts some excessive assurances to remove to depollute.

The key of any distillating method is to distill in the distillation equipment of the cleanest as far as possible, minimum pollution.Get rid of oxygen and any external or system's organic contaminant is desirable especially.It is found that, when enforcement is of the present invention, improves sealing and be easy to remove parts, use grease in order to provide, comprising fluoridizing grease, for example the normally used grease of fluoridizing in distillation and vacuum system may pollute the distillation here, is enough to reduce actually absorptivity.Therefore, most preferably in " no grease " Distallation systm, carry out this distillation." no grease " used herein when being illustrated in the cleaning member of this system of assembling, do not use grease.Those skilled in the art should know that term " no grease " does not also mean that the present invention is exactly exercisable if there is a small amount of grease contamination in some place of this system.Can remove all grease contamination with regard to this system, advantageously reduce the absorptivity of liquid alkane, still " no grease " do not plan requirement fully without any grease, no matter how little concentration is.

High transparent liquid alkane has multiple use in wavelength coverage 170-260nm.Expection is used and to be included but not limited to optical coupled agent, optical cement, optical element, for example liquid lens, be used for the index-matched optical check medium of semiconductor wafer and device, and immersion liquid, 193 and the 248nm photoetching process especially true.

Preferably, the refractive index of liquid alkane is 1.5-1.7, more preferably 1.6-1.7.

In many cases, usually in fact buy the liquid alkane of high-purity distillation level, using for example processing of silica gel absorber is the purification step of unique needs, for some application, may wish to adopt analytical approach (for example gas chromatographic analysis/mass spectroscopy) to identify pollutant, learn so that better develop purification process.Can adopt known decontamination method, but avoid enforcement method very preferably under the clean conditions that further pollutes.

Injection is a kind of appropriate method of removing the alkane pollutant, especially removes the appropriate method of deoxidation.A kind of injection method that can adopt is following method: for glove box provides steel cylinder dress high-quality nitrogen that dry low oxygen content nitrogen (for example 99.998%), Matheson sell or by boiling off the high-quality nitrogen that liquid nitrogen obtains.The about 10ml liquid aliquot of dress in 20ml glass scintillation pipe.This sample transfer in the nitrogen purge drying box, is guaranteed that this pipe is flat at working surface; Take the vinyl cover of pipe, tractable glass pipette drops in the solvent, then by passing through this suction pipe supplying nitrogen with the same dry low oxygen content source of the gas of glove box.Regulate flow velocity, keep the fierce bubbling of solvent, only otherwise solvent is spilt outside the pipe.The strong injection 30-60 second, its time looks is enough to obviously reduce oxygen content and possible liquid water content, and does not make liquid alkane that bigger vaporization loss is arranged.

Because can adopt the sensitivity limit of instrument is about 1ppm oxygen, the actual oxygen concentration of sample may be more much lower than 1ppm.Utilize Henry's law, adopt existing henry 's law constant in the document, can estimate the oxygen concentration in the cyclohexane.Suppose that in each case the atmosphere of liquid alkane and headroom is in balance, for calculating purpose, the atmosphere of this headroom is made up of nitrogen and the oxygen partial pressure of pointing out.

Table 4

The dissolved oxygen DO that in cyclohexane, calculates

O2 dividing potential drop on the cyclohexane	Be dissolved in the calculating O2 in the cyclohexane
		0.38 holder O2 (1 atmospheric pressure N2 on the cyclohexane that contains 500ppm O2)	0.22ppmw
0.38 holder O2 (1 atmospheric pressure N2 on the cyclohexane that contains 50ppm O2)	0.02ppmw
		0.0076 holder O2 (1 atmospheric pressure N2 on the cyclohexane that contains 10ppm O2)	0.004ppmw
0.0038 holder O2 (1 atmospheric pressure N2 on the cyclohexane that contains 5ppm O2)	0.002ppmw
		0.21 holder O2 (1 holder pump vacuum: i.e. 1 holder air on the cyclohexane)	0.12ppmw
1.05 holder O2 (5 holder pump vacuum: i.e. 5mm air on the cyclohexane)	0.61ppmw

The blanket of nitrogen of handling these samples in these examples produces by boiling off liquid nitrogen, estimates that oxygen concentration is 3-5ppm.As table 4 as can be seen, this is corresponding to about 0.002ppm oxygen in cyclohexane.This concentration is significantly less than preferred upper limit 2ppm oxygen of the present invention.

But a system of selection of this liquid alkane of purifying is the decompression distillation (bulb-to-bulb distillation) by the 3A molecular sieve bed.For example, connect two flasks by the aforesaid pipe that preheating 3A molecular sieve is housed.One of them flask part cargo shipment liquid to be purified seals this system more then.This liquid is removed the oxygen of dissolving through three freezing/fusing circulations.After freezing this liquid once more with liquid nitrogen then, this system is emptied completely.This system seals under vacuum, and cooled with liquid nitrogen is bathed and transferred to the sky flask from the flask that liquid is housed.When liquid was heated to room temperature, its distillation arrived in the cooling flask by the 3A molecular sieve bed.In case distillation is finished, remove vacuum with the nitrogen of anaerobic, allow the liquid of purifying be heated to room temperature, this flask closes valve for future use then.

From the viewpoint of practicality, it is very desirable removing the pollutant with photochemical reaction.Such material not only is easy to strong absorption at the wavelength zone of 170-260nm, and can also stand light-induced reaction, usually causes forming bubble and liquid alkane blackening.It all is useful extracting any photochemical activity material, no matter whether extract any other photochemical activity material of existence.

In a specific embodiments of the present invention, it is bright that all surfaces may be launched illumination.But preferably, this surface is become image exposure, and some parts exposes, and other parts are unexposed.Preferably, this surface is immersed in the liquid alkane.

In a preferred specific embodiments, in immersion lithography process, at wavelength coverage 170-260nm, preferably 193nm or 248nm most preferably use this liquid alkane in the 193nm.In this specific embodiments, the photoresist surface targets is immersed in the liquid alkane at least.The liquid that is applicable to immersion lithography process is preferably transparent, is enough to make operating distance at least 10 ' the s micron, at 193nm irradiation stability is arranged.The transparency of liquid alkane, refractive index and irradiation stability combine, and make it be specially adapted to immersion lithography process at the 193nm exposure wavelength.

This alkane is compatible with the other materials that physically uses with this method at chemistry also to be very preferred.In the immersion lithography process of 193nm exposure wavelength, allow immersion fluid contact with the photoresist polymkeric substance.It is desirable to very that this immersion fluid does not dissolve or the swelling photoresist, do not disturb under the 193nm exposure and in photoresist, form sub-image, do not disturb the development of photoresist of photoimaging in developer solution subsequently.In addition, this immersion fluid preferably has enough low volatility, does not therefore need it is contained in the pressure vessel, and can take out before oven dry after the exposure and development and reprocess.

During this immersion fluid infringement resist, external coating is necessary.Preferably, suitable external coating in wavelength coverage 170-260nm, particularly 193 and 248nm be fully transparent, be the photochemistry inertia in such wavelength coverage, basically be insoluble to this liquid alkane, and be dissolved in the insoluble solvent of photoresist.Therefore, use this matrix of photoresist spin coating, and the matrix of coating spin coating external coating then allows this spin coating matrix contact with liquid alkane.Carry out photoimaging then, according to those skilled in the art's known method, by be dissolved in do not dissolve or the solvent of swelling photoresist in remove external coating, make development of photoresist.

In some method, liquid alkane stands the reirradiation of intense laser pulse string, and contacts with other surfaces, and still, these clean surfaces still may contain some pollutant.As time goes by, these two kinds of influences can both damage the absorptivity of liquid alkane.People find, preferably under inert atmosphere, allow this liquid alkane carry out circulation by for example adsorbent noted earlier, it can be returned to absorptivity and be lower than 1cm ^-1Can be interrupted or carry out continuously the circulation and the regeneration of liquid alkane.

In a preferred specific embodiments, a kind of method also comprises the closed loop cycle system that handles and add liquid alkane continuously again that uses.The specific embodiments of such circulation system is listed in Figure 17.Figure 17 has shown " optics ledex ", and it is also referred to as " photoscanner " 1, and wherein photoresist places on the silicon wafer 2, and imaging.From the light of light source (for example 193nm ArF excimer laser) optically by illuminator 3 homogenising, this rayed photomask 4, the projection lens 5 of light by many single lens elements are arranged usually then, and image reduces 4 or 5 times.In projection lens bottom " spray head " 6 arranged, it is coupled together the last lens element of this projection lens and the wafer of immersion fluid and painting photoresist, thus on the light path of this light without any the conciliation air gap.This spray head is filled immersion fluid, and for example liquid alkane 7, and immersion fluid contacts with the silicon wafer 2 that scribbles photoresist with the last lens element of projection lens, and silicon wafer 2 will receive photomask pattern.The silicon wafer of painting photoresist also may comprise Topcoating, and it is on the photoresist layer, and can be used for immersion fluid and photoresist are separated.So name " spray head " is because it can play in the optics ledex and provide and return mobile immersion fluid, catches the effect that flows to the immersion fluid that does not need the zone in the optics ledex.In this specific embodiments, liquid alkane 7 is from reservoir 8, by transmissive tube 9, the reservoir 10 of absorbent particles is housed, enter spray head 6 continuously, absorbent particles for example is activated silica gel, aluminium oxide, charcoal, zeolite, most preferably their potpourri.This reservoir cleans with inert gas continuously by charging aperture 11, discharges from escape hole 12 again.In addition, reservoir can effectively spray.Liquid alkane is added to spray head continuously, passes through circulation pipe 13 more continuously from wherein discharging.This circulation pipe is added to one group of three kinds of inert atmosphere 14 to liquid alkane, fills in the cleaning post 15 of adsorbent, and these posts also can effectively spray.When leaving last post, circular flow is by comprising the online ultraviolet spectrometer (UVS) of light source and detector, and it preferably is determined at the absorptivity 16 of photoetching process wavelength, thereby measures the optical absorptivity of handling immersion fluid again.This circular flow is directly turned back in the reservoir 9 again.Can make immersion fluid pass through spray head by reservoir, in every way, for example adopt the pump (selecting to make) of peristaltic pump and so on, to flow through this system by purification column with the non-polluting material, perhaps depress and service property (quality) stream or liquid flow control device, allow this immersion fluid flow at indifferent gas.

Imagined 193 and the 248nm exposure wavelength under three preferred specific embodiments in the immersion lithography process framework.They are contact, approaching and projection immersion lithography process.In the projection immersion lithography process, liquid refractivity has the effect that effective reduction laser wavelength of incidence is provided, wherein λ _{Immersion fluid}=λ _Vacuum/ n _{Immersion fluid}, λ is respectively an optical maser wavelength in immersion fluid or the vacuum in the formula, n is the refractive index of immersion fluid.Effectively reduce exposure wavelength and cause image resolution ratio to be improved, available image is littler.

In contact with near immersion lithography process, for example 193 and the 248nm exposure wavelength, the laser wavelength of incidence in the fluid is identical with the projection immersion lithography process, but imaging size determines by the contact of use or near mask.In contact or near immersion lithography process, first purpose of liquid alkane is the pollution that the protection imaging surface is not subjected to particle for example or ambient dust.In addition, be used for when determining candidate's liquid serviceability of more complicated, more expensive but preferred projective techniques contact or be useful screening technique near immersion lithography process.

In a specific embodiments, by the 193nm radiation of photomask transmission from for example ArF excimer laser, this photomask comprises employing electron beam patterning method usually at the chromium metallic circuit figure pattern that carves on glass, therefore forms the circuit pattern image on photoresist.Many materials as photoresist are that people are known in the art, and have the wide range of commercial purposes.All like this some materials all be suitable for implementing the present invention, as long as they are to the 193nm photaesthesia, and be insoluble to basically in the alkane, can prevent that perhaps it from being dissolved by external coating.L.F.Thompson, C.G.Willson and M.J.Bowden " micro-lithography method introduction ", the 2nd edition, American Chemical Society, suitable photo-corrosion-resisting agent composition 1994, has been described in the Washington D.C..Suitable photoresist example comprises Rohm and Haas ElectronicMaterials (Marlborough, MA.) 193nm Epic Resists, perhaps some companies, TOK (OHKA AMERICA for example, INC.Headquarters/Hillsboro, Oregon, or AZ Electronic Materials, Somerville, other resists of NJ.

Just processing photoresist, for example Rohm and Haas ' s Epic 2200 and negative processing photoresist, Rohm and Haas ' s UVN30 for example, the both is applicable to the immersion lithography process method.Just processing photoresist is a kind of like this photoresist, and wherein the exposure area becomes and dissolves in the developer, and unexposed area is insoluble to wherein.Negative processing photoresist is a kind of like this photoresist, and wherein the exposure area becomes and is insoluble in the developer, and unexposed area is dissolved in wherein.

When photoresist becomes the exposure of image ground, form so-called latent image.In a specific embodiments of the inventive method, use the chemistry that contains light acid propellant (PAG) to strengthen positive resist.The photoresist layer that comprises latent image stands postexposure bake (PEB) step and reaches 60 seconds usually under air and temperature 90-140 ℃.After the PEB step, the silicon wafer of painting photoresist is put into alkaline aqueous developer again, 0.26 Normal TMAH developer for example, and develop in the exposure area of polymer film whereby, observes the photoresist of forming pattern.

When sign was used for the photoresist performance of photoetching process method, it was E that two useful exposure parameters are adopted in the present technique field ₀, remove the required open grid exposure dose of photoresist, and E ₁, produce and require the required minimum dose of image.E ₀Sometimes be called removing dosage, and E ₁Be called the gluing dosage that obtains the reasonable size figure.

The thickness of photoresist layer is during without any special restriction, and in typical case of the present invention implemented, the photoresist coating thickness on the silicon wafer substrate should be 150-200nm.This thickness is by the minimum feature size decision that requires to print.For this notion is described, but the scope of the present invention is not had any restriction, use aspect ratio 3-4, a representative value in the semiconductor technology, if the eigenwert that requires is wide 65nm, film thickness should be～195nm.Generally speaking, the photoresist layer is thick more, and anti-dry ecthing method is just good more in the subsequent treatment of forming pattern photoresist layer.

External coating exist in the operability that can not change immersion lithography process in essence.Suitable external coating includes but not limited to high transparent fluoropolymer, and they are dissolved in the fluorated solvent, but the solvent that they neither the photoresist polymkeric substance.Particularly preferably be amorphous (per) fluoropolymer, for example the Teflon  AF of DuPont.In typical application, dissolve unformed fluoropolymer, reach at perfluorinated solvents (Fluorinert for example ^TMFC-75) concentration in is 1-5 weight %.The solution of making like this is spin-coated on the matrix of painting photoresist, forms the outer coating film of thickness 50-300nm.

Those skilled in the art should know, 193nm radiation source or wavelength coverage 170-260nm radiation source and non-critical value.The ArF excimer laser is convenient, controlled high density 193nm radiation source, so it is preferred.

Fig. 4,5 and 6 has described the photolithographic specific embodiments of the present invention.Fig. 4 has shown complete system, and its parts advantageously are placed in the nitrogen drying case 1, the optical table 2 of regulating optics is housed in the drying box and shifts example platform.Scientech power meter 3 is used to read the 193nm pulsed laser energy of ArF excimer laser 4 emissions.In a specific specific embodiments shown in Figure 4, the photoetching process exposure room is hypoxemia/low humidity nitrogen wash drying box (Nexus Dry Box, Vacuum Atmospheres Co., Hawthorne CA90250-6896), it is applicable to device as herein described.193 and 248nm laser be incorporated in this drying box by entering hole 5.The drying box control panel that inner oxygen and water analysis instrument 6 are installed is used for monitoring the oxygen content of drying box, and is used in reference to be shown in after adding sample when oxygen concentration reduces the acceptable level that reaches.When being incorporated in the drying box chamber, fusing silicon dioxide beam splitter 8 reflexes to laser beam 7 downwards the silicon wafer 9 of painting photoresist.The wafer of painting photoresist is contained in the aluminum frame of machining, and the about 1mm of submergence is dark in liquid alkane.Whole plate can shift under laser beam, allows the wafer of different piece be subjected to the sequential exposure of different exposure doses.

Fig. 5 shows the optical exposure system of Fig. 4 in greater detail.The pulse laser beam 7 of excimer laser 4 enters drying box 1 entering hole 5, pass manual operation shutter 10, reenter and be mapped on the fusing silicon dioxide beam splitter 8, it reflexes to the fraction laser energy downwards on the silicon wafer 9 that is installed in the painting photoresist on the translator, and this converter can make sample shift under laser beam.Main laser beam continues across beam splitter 8, is incident on the power gauge outfit 3 again.

Fig. 6 shows the silicon wafer exposure desk, the silicon wafer 11 of the laser light strikes of excimer laser in machining aluminium sheet 12 wherein, and aluminium sheet 12 moves along the converter platform on Fig. 4 optical table 2 under laser beam, so that can be with various exposure dose sequential exposures.The 13rd, the N2 environment of N2 drying box.The 11st, silicon wafer, it has been coated with as following photosensitive photoresist polymkeric substance 14 discussed in detail.Do not show the external coating that discuss the front.Fig. 6 A describes is a specific embodiments at the contact immersion lithography process of 193nm exposure wavelength, wherein photomask 15 places on the photoresist polymeric layer surface, add immersion fluid, the silicon wafer that covers painting photoresist reaches the about 1mm 16 of the degree of depth.When having found that photomask is small and light,, be at first to add immersion fluid easily, photomask be positioned in this fluid and on the silicon wafer surface of painting photoresist more for example as the metal grill that is used for this paper specific embodiments.Fig. 6 B has illustrated identical configuration, but does not have immersion fluid; Fig. 6 B is not a specific embodiments of the present invention.

In another specific embodiments of the present invention, photomask can be offset the about 10 μ m of distance on photoresist surface.In a preferred specific embodiments of the present invention, in the projection photoetching process of so-called 193nm exposure wavelength, photomask place light path some make things convenient on the position, and image scioptics system typically is referred to as projection lens, is projected on the photoresist.This optical projection system provides the highest resolution for each specific embodiments of the present invention.

In another preferred specific embodiments of the inventive method, adopt the projection photoetching process of 193nm exposure wavelength.In this specific embodiments, output element-the lens combination of projecting lens that end nearest-place liquid alkane from photoresist surface, apart from the about 0.5-5mm in photoresist surface, it also is immersed in the liquid alkane, and the photoresist surface randomly has the external coating of thickness 50-200nm.In this specific embodiments, reduce the effective wavelength of incident light, thereby the image resolution ratio raising has surpassed the image resolution ratio that can reach in gas atmosphere.

Determine the thickness of liquid alkane layer according to the particulars of development or use imaging system.For example, in the contact lithograph method of 193nm exposure wavelength, suitable liquid alkane submergence layer thickness is 1mm.1mm also can be suitable for scanning or stepping wafer under the projection lens, keeps enough distances simultaneously between projection lens output element and wafer.Those skilled in the art should know, along with immersion fluid thickness increases, optical attenuation also can increase thereupon, but the tolerance of stepping or scanning machinery becomes and edges down.Thinner immersion fluid layer may allow higher exposure, may become undue harsh but reach at a high speed with the tolerance that high precision scans and/or the stepping wafer is required.

This liquid alkane has very perfect performance combination.Preferably, it is easy-to-handle low-viscosity (mobile) liquid.It has desirable low absorptivity at 193nm, and in preferred specific embodiments, absorptivity is 0.1-2cm ^-1In a specific embodiments very preferably, alkane in the absorptivity of 193nm less than 0.5cm ^-1, refractive index is 1.4-1.7.

This liquid alkane provides adaptability for system design, has reduced the requirement that submergence layer thickness and Machine Design is reached balance.

In a complete semiconductor production process, repeatedly carry out photoetching process imaging and photoresist layer in order and develop, a series of photomask patterns and various etching and deposition process are arranged between continuous photolithography steps.

Except that as the immersion fluid in the photoetching process, can adopt multiple mode to utilize liquid alkane.Other application example comprise alkane wherein place 193 or 248nm light source and target between application.Pure alkane can be as the index-matched liquid in the liquid lens etc., or it can be the component of potpourri or thinning agent, for example solvent of polymkeric substance, the plastifier of thin polymer film in the spin coating operation, or the solvent in the adhesive formula.In another embodiment, alkane can be used for the article that optical check forms pattern or do not form pattern, and for example semiconductor wafer detects the tiny defect that changes optical property here.The immersion fluid that alkane is checked as submergence, can be in this be checked high-resolution imaging more, can reduce light scattering again from the sample profile, can check for example possible defective dark hole, for example the particulate fragment of Cun Zaiing.In another embodiment, this liquid alkane is used to produce thin plate, layer, coating and film, and they are applicable to the photolithographic lens of 193nm, photoconductive tube, antireflecting coating and layer, window, protective finish and glue.

This liquid alkane also can be used for the element of compound lens, and the design compound lens is used to reduce aberration.Before this, have only CaF2 or may be counted as having enough transparencies by the hydroxyl free silica, be used for the transmission focusing element at 193nm.As for example R.Kingslake, Academic Press, Inc., 1978, the 77th page of " lens design basic principle " (LensDesign Fundamentals) is disclosed, and people also know by using second kind of material of different refractivity and chromatic dispersion, can make achromat.By using liquid alkane and CaF ₂, expect to use described this or other analog materials of the application, can make achromat.

To further specify the present invention, but be not limited to following specific specific embodiments.

Embodiment

Absorptivity is measured

(Harrick ScientificCorporation 88 Broadway Ossining, NY) the removable liquid cell of DLC-M13 type are measured transmission base absorptivity to use Harrick Scientific Corp. shown in Figure 1.There is a 8mm fenestra in this pond, and it comprises (2) 13mm diameter * 2mm thickness C aF ₂Window, Viton  O-annular seal, the Luer-Lok  joint (fitting) of (2) dress sample, various Teflon  pads, its thickness 6-4000um.DLC-M13 is installed in the spectroscope ellipsometer of variable-angle, and it is J.A.Woollam Co., Inc., and Lincoln, NE produces, or VUV-Vase ^The VU-302 type, it is used for the measurement of nearly IR to 145nm, or DUV-Vase ^The V-type, it is used for the measurement of nearly IR to 187nm.As shown in Figure 1, fluid sample to be tested is placed in the pond, and this pond is by parallel CaF2 window and the Teflon (r) that inserts between these windows ^Ring constitutes.As long as the multiple optical path length by branch same sample such as differences is provided, just can use Teflon (r) the  ring of 6,25,100,500,920,2200,3000,4000,6000 and 10000 micron thickness.The pond when filling with substance is noted avoiding in the 8mm diameter window fenestra bubble being arranged.

For the purposes of the present invention, as the optical absorptivity A (cm of equation 1 defined every centimetre of thickness of sample ^-1), be defined as CaF ₂Window in the transmission of tested wavelength divided by the ratio denary logarithm of test specimen (window adds the test sample) in the transmission of this wavelength, divided by the thickness (t) of test specimen-under the situation of the experiment of this paper report, or 6,25,100,500,920,2200,3000 or 4000 microns as previously discussed.

Equation 1

In order to eliminate the multipath reflection influence of using under the fluid sample situation here, use the Harrick pond that different ponds spacer thickness is arranged, the transmission of adopting this pond to fill multiple liquid changes relatively determines absorptivity.For example, measure the spectral transmission (t of two pond thickness for two different pond thickness ₁And t ₂), and transmission (T ₁And T ₂) increase and increment reduces with the sample optical path length, user's formula 2 obtain absorptivity/centimetre.

$A/\mathrm{cm}=\frac{{\log }_{10}\left(T_1\right)-{\log }_{10}\left(T_2\right)}{t_2-{\mathrm{<figure-callout\; id="1"\; label="t"\; filenames="A20058001790700501.png"\; state="\{\{state\}\}">t</figure-callout>}}_1}$

Equation 2

We have summed up this relative transmission method of being measured absorptivity by multiple optical path length in the sample, so that reach better degree of accuracy when measuring the optical absorptivity of every centimetre of these materials.We use up to 5 different optical path lengths, scanning 6-4400 micron pond thickness.In this case, we have measured the transmission T in all thickness pond _n(generally) is with thickness t _nVariation.

$T_1\left(\mathrm{\&lambda;}\right)=T_0\left(\mathrm{\&lambda;}\right)e^{-\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right){\mathrm{<figure-callout\; id="1"\; label="t"\; filenames="A20058001790700501.png"\; state="\{\{state\}\}">t</figure-callout>}}_1}$

$T_2\left(\mathrm{\&lambda;}\right)=T_0\left(\mathrm{\&lambda;}\right)e^{-\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right){\mathrm{<figure-callout\; id="2"\; label="t"\; filenames="A20058001790700501.png,A20058001790700521.png"\; state="\{\{state\}\}">t</figure-callout>}}_2}$

$T_3\left(\mathrm{\&lambda;}\right)=T_0\left(\mathrm{\&lambda;}\right)e^{-\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right){\mathrm{<figure-callout\; id="3"\; label="t"\; filenames="A20058001790700501.png"\; state="\{\{state\}\}">t</figure-callout>}}_3}$

…

$T_n\left(\mathrm{\&lambda;}\right)=T_0\left(\mathrm{\&lambda;}\right)e^{-\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right)t_n}$

Then all equations are taken the logarithm and obtain:

lnT ₁(λ)＝lnT ₀(λ)-α(λ)t ₁

lnT ₂(λ)＝lnT ₀(λ)-α(λ)t ₂

lnT ₃(λ)＝lnT ₀(λ)-α(λ)t ₃

…

lnT _n(λ)＝lnT ₀(λ)-α(λ)t _n

This is a cover linear system y _i=ax _iThe N an of+b equation, y in the formula _i≡ InT _i(λ), a ≡-α (λ), b ≡ InT ₀(λ) and x _i≡ t _i

We use linear algebra, adopt the absorption of sample rate/centimetre least square method, solve this linear equation system simultaneously.Error at measurment and the irrelevant situation of i (same variance) for all observed results, adopt these equations of least square solution, and the error of measurement result adopts weighted least-squares method to separate these equations when relevant with i (different variance), and the two is all separated.

As with variance situation example, the equation that we separate is:

$\frac{\&PartialD;}{\&PartialD;a}\mathrm{\&Sigma;}{(\ln T_i\left(\mathrm{\&lambda;}\right)+\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right)t_i-b\left(\mathrm{\&lambda;}\right))}^2=0$

$\frac{\&PartialD;}{\&PartialD;b}\mathrm{\&Sigma;}{(\ln T_i\left(\mathrm{\&lambda;}\right)+\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right)t_i-b\left(\mathrm{\&lambda;}\right))}^2=0$

And separate be:

$\mathrm{\&alpha;}\left(\mathrm{\&lambda;}\right)=\frac{\mathrm{\&Sigma;}{t}_i\mathrm{\&Sigma;}\ln T_i\left(\mathrm{\&lambda;}\right)-\mathrm{N\&Sigma;}{t}_i\ln T_i\left(\mathrm{\&lambda;}\right)}{\mathrm{N\&Sigma;}{t}_i^2-\mathrm{\&Sigma;}{t}_i\mathrm{\&Sigma;}{t}_i}$

$b\left(\mathrm{\&lambda;}\right)=\frac{\mathrm{\&Sigma;}\ln T_i\left(\mathrm{\&lambda;}\right)\mathrm{\&Sigma;}{t}_i^2-\mathrm{\&Sigma;}{t}_i\ln T_i\left(\mathrm{\&lambda;}\right)\mathrm{\&Sigma;}{t}_i}{\mathrm{N\&Sigma;}{t}_i^2-\mathrm{\&Sigma;}{t}_i\mathrm{\&Sigma;}{t}_i}$

By this repeatedly transmission measurement analysis of many times of pond thickness material, we can measure the absorptivity of material/centimetre.

Harrick pond cleaning and number of assembling steps:

Before using and after each sample preparation, the Harrick pond uses Vertrel  XF as cleaning solvent (Miller-Stephenson Chemical Co., Danbury, CT) flushing.Female Luer-Lock joint (the Becton Dickinson of cleaning 1ml glass syringe, FranklinLakes NJ), it fills Vertrel XF, links to each other with Harrick pond Shangyang Luer-Lock joint then, at this moment allows Vertrel XF wash by this pond.At this moment this pond dries up with " housenitrogen " (liquid nitrogen obtains by boiling off, and it contains following water of 3ppm and the following oxygen of 5ppm).This pond is according to assembling with reverse order shown in Figure 1 then.The Teflon of CaF2 window and selected thickness ^Pad is contained in the 20ml bottle that Vertrel  XF is housed, and covers tight bottle, is put into 30-60 second in the ultrasonic bath then.From Cleaning bottle, take out CaF ₂Window and pad are used Vertrel at last ^The Q-tip wiping that XF is wetting is then with the air blow drying that blows up a balloon.Then, assembly as shown in Figure 1 according to shown in the order vertical stacking assemble this pond, with hand compression nut is screwed on the pond.In laboratory fume hood, under air, clean and assemble.

Dress Harrick pond in air ... (laboratory fume hood)

With the 1ml BD glass syringe of cleaning, about 0.5ml sample liquids to be transferred to the ready pond like this from its container, this syringe links to each other with the pond then, and its liquid is adorned in past this pond, up at top Luer-Lok ^See liquid meniscus above the joint, therefore can not allow any voids to stay in the fenestra in pond.Cover top Luer-Lok  joint with Teflon  stopper then, the reversing pond, its pond still links to each other with syringe.Turn on syringe, cover the joint in the pond of exposure like this with another Teflon  stopper.

Dress Harrick pond in nitrogen ... (nitrogen drying case)

The pond of prosthomere cleaning and assembling is put into 100 Series P lexiglass glove box (TerraUnversal, Anaheim CA) N2 purifies in the cup, perhaps be put into and nitrogen purge Nexus100043 type drying box (Vacuum Atmospheres Co., Hawthorne is CA) in the continuous cell with the nitrogen flushing.With house nitrogen cup was washed about 30 minutes continuously, the oxygen gauge on drying box is read 10ppm O ₂The emptying cell, inflated with nitrogen is 3 times then, again this equipment is transferred to drying box.

For example prosthomere is described, adopts the mode that adds sample to the Harrick pond.

In nitrogen, dry sample is installed in the Harrick pond ... (nitrogen drying case)

In described mode, (separate having Teflon  stopper; Do not insert) cleaning assembling pond, clean 1ml BD syringe and being put in the previously described drying box with the sample of selecting of adsorbent drying in sample bottle still.

Open sample bottle, this liquid is poured in the clean 15ml BD syringe that has 0.45 micron PTFE Luer-Lok  filtrator.Use syringe this liquid to be transferred in clean, the dry 20ml bottle by filtrator.The sample transfer of about this spline filter of 0.5ml in pond as described above.

The mensuration of absorptivity

For the purpose of embodiment below this paper, the absorbed rate when adopting above-mentioned relative transmission method to measure various ponds thickness.Adjust the thickness of test specimen, so that it is reach absorptivity at least 0.1%, identical thereby the error at measurment of a plurality of samples keeps.

Also adopt Varian Cary 5UV/Vis/NIR spectrometer directly to measure absorptivity.The relative transmission measurement result that the unitary determination result of VarianCary 5 measures not as a plurality of optical path lengths that use the VUV-Vase ellipsometer is such when accurate, and the time that obtains data consumes is wanted much less.

The measurement of refractive index

Use VUV-vase and DUV-vase instrument (for example referring to people such as Burnett, " CaF ₂, SrF ₂, BaF ₂With absolute index of refraction and the hot coefficient of LiF at nearly 157nm "; " Appl.Opt. " 41; people such as 2508-2513 (2002) and French; " using the immersion fluid refractive index of prism minimum deflection technology "; " Optical Microlithography ", XVII, SPIE5377-173; (2004)), adopt additional Fig. 2 and the illustrated minimum deflection prism method of Fig. 3 to measure the refractive index and the temperature coefficient thereof of this material.

In order to measure as the fluid refracting rate that is used for the immersion fluid candidate thing of photolithographic processes, the prism pond of having used filled with fluid.This pond is an equilateral stainless steel liquid prism, and it comprises the CaF of two diameter 12.7mm * thick 2mm ₂Window and Viton ^The Luer-Lok  joint of O-ring packing, dress sample.Taking this pond apart cleans.

Before each the use, the 1mlBD glass syringe is all used in this pond,, washes and removes former sample with Vertrel  XF flushing by two Luer-Lok  joints.Then, drying is carried out with the air that air blows up a balloon in this prism pond.Taking the pond again apart cleans.In the sealed tube that Vertrel  XF is housed, stir cleaning CaF2 window and stainless steel pond body 30-60 second by ultrasound wave.After the CaF2 window takes out, use the moistening cotton swab wiping of Vertrel  XF again from ultrasonic bath, then with the air drying that blows up a balloon.After taking out, the pond body uses the air drying that blows up a balloon again from Cleaning bottle.And then assemble this pond.

Dress prism pond in nitrogen ... (nitrogen drying case)

In mode described above,,, be put in 100 Series P lexiglass glove boxes or the Nexus 100043 type drying boxes with Teflon  stopper (separate, not insert), clean 1ml BD syringe and the specimen material of selection the assembling pond of cleaning.

Open sample bottle, from this sample bottle, take out about 1ml sample (this fluid filters with 0.20 micron PTFE filtrator), then carry out previously described method at this paper.

In nitrogen, pack in the prism pond silica gel or 3A dry-eye disease (nitrogen drying case)

In the mode of describing, cleaning assembling pond, with Teflon  stopper (separate, do not insert), clean 1ml BD syringe with still in sample bottle, put into above-mentioned drying box with the selected specimen material of silica gel or 3A molecular sieve drying.

Open sample bottle, liquid is poured in the clean 15ml BD syringe that has 0.2 micron PTFE Luer-Lok  filtrator.Use this syringe, this liquid is transferred in the clean dry 20ml bottle by filtrator.The such filtered sample of about 1ml is transferred to as previously described in the pond.

The minimum deflection index method

Equilateral liquid prism is contained on the VASE  its configuration control computer, stepper motor driven θ-2 θ incident angle platform.This prism is contained on as shown in Figure 3 the sample stage.In the mensuration process, control sample universal stage and detector arm universal stage respectively.Use monochromator to select by the target wavelength λ of VUV near infrared (NIR).The angle of detector arm scanning certain limit under the condition of certain wavelength and incident angle is comprising expectation transmission angle, so that accurately measure the transmission angle.Multiple scanning certain limit incident angle is comprising this process of expectation minimum deflection angle.In case determine the minimum deflection angle, can determine index n by equation 3 _Mat(θ), α=prism vertex angle in the formula, the minimum deflection angle of δ (λ)=mensuration, n _Gas(λ)=N ₂Environmental index, n here _Nitrogen=about 1.0003.

Equation 3

The VUV-VASE ellipsometer is used to be determined at the index under 32 ℃ of the nominal temperatures.The DUV-VASE ellipsometer is used to be determined at the index under 22 ℃ of the nominal temperatures.

The material that adopts

			Teflon TM?AF 1601，	Tetrafluoroethene/4,5-two fluoro-2, two (trifluoromethyl)-1 of 2-, 3-dioxole multipolymer	DuPont，Wilmington， DE.
				76: 24,4,5-two fluoro-2, two (trifluoromethyl)-1 of 2-, 3-dioxole/perfluoro propyl vinyl ether copolymers	WO 01/37043 described method
				60: 40 hexafluoropropylenes/: TFE copolymer	US 5,478,905 described methods
			Cytop TM: (per) fluoropolymer	Perfluorobuttene base vinyl ether copolymers	Asahi?Glass，Chadds Ford，PA.
			FLUORINERT TM FC-75，	Perfluor ether liquid	3M，Minneapolis，MN
			FLUORlNERT TM FC-40，	Perfluoroamine liquid	3M，Minneapolis，MN
			Performance Fluid?PF-5080，	Perfluoroalkane liquid	3M，Minneapolis，MN
Vertrel TM?XF	2,3-dihydro perflenapent	DuPont

The device that uses

In bag glove, glove box and drying box, carry out the following work of this paper.Bag glove is the polyolefin bag, and it has the gloves shaping annex that is used to operate and is adopting method for folding to make the rough seal of bottom.Glove box is a kind of self-control case, and this case is that the PMMA boxboard is sticked together, and the common drying box gloves of installation are made like this outside this case.This drying box is the commodity drying boxes, has higher quality seal part and chamber door, and Henry's law is applied in the nitrogen oxygen concentration up to 100ppm, still produces the dissolved oxygen DO that parts per million (ppm) is only arranged.We also do not see any experimental evidence that adopts special shell to cause Different Results, and therefore, several terms mentioned in this article are commutative to a certain extent.

The comparative example 1

Adopt minimum deviation method previously discussed to measure the refractive index of deionized water, conductivity is 17.5 megaohms.32 ℃ of refractive indexes in 193nm is 1.433, is 1.377 at 248nm.22 ℃ of refractive indexes in 193nm is 1.436, is 1.378 at 248nm.

Embodiment 1

A. the absorptivity of primary sample cyclohexane (Fluka catalogue #28935, the purity 99.5% that adopts GC to obtain, boiling point 80-81 ℃).According to previously described relative transmission beam method, recording at 193nm is 4.78cm ^-1

B. dry molecular sieves (3A) 2 hours under 350 ℃ of air.Allow the so dry molecular sieve of about 10 grams mix with 20ml primary sample cyclohexane.Remove by filter molecular sieve under N2 in glove box after, the cyclohexane that adopts relative transmission method to record processing like this is 2.14cm in the absorptivity of 193nm ^-1

C. dry silica gel (Aldrich catalog number (Cat.No.) 24,982-3,3.8 order classes) two hours under 500 ℃ of air.In 20ml primary sample cyclohexane, add for example this dry silica gel of about 10ml.Remove by filter silica gel in glove box under N2, the cyclohexane that adopts relative transmission method to record processing like this is 0.14cm in the absorptivity of 193nm ^-1

D. adopt minimum deviation method previously discussed to measure the refractive index of cyclohexane.22 ℃ of refractive indexes in 193nm is 1.571, is 1.494 at 248nm.32 ℃ of refractive indexes in 193nm is 1.56, is 1.48nm at 248nm, as table 2 and shown in Figure 9,

E. dry aluminium oxide (Aldrich catalog number (Cat.No.) 30,911-7, granular, 4-8 order) two hours under 500 ℃ of vacuum.In 15ml primary sample cyclohexane, add this aluminium oxide of about 5ml.In glove box at N ₂Under filter aluminium oxide after, the cyclohexane that adopts relative transmission method to record processing like this is 0.35cm in the absorptivity of 193nm ^-1

Embodiment 2: cyclopentane

A. according to this paper relative transmission beam method previously discussed, (Fluka (catalogue #29682, the purity 99.0% that adopts GC to obtain, 50 ℃ of boiling points) is 0.42cm in the absorptivity of 193nm to the primary sample cyclopentane ^-1

B. the dry molecular sieves (3A) that allows about 10g prepare in embodiment 1 is mixed with 20ml primary sample cyclopentane.In glove box at N ₂Under remove by filter this molecular sieve after, the cyclohexane that adopts relative transmission method to record processing like this is 0.37cm in the absorptivity of 193nm ^-1

C. about 10ml dry silica gel and 20ml primary sample cyclopentane that allowing provides as embodiment 1 merge.In glove box at N ₂Under remove by filter this silica gel after, the absorptivity 193nm that adopts relative transmission beam method to record the cyclohexane that sample handles is 0.30cm ^-1

D. adopt minimum deflection prism method previously discussed to measure the refractive index of cyclohexane.As table 2 and shown in Figure 11, be 1.46 32 ℃ of refractive indexes in 248nm.

Embodiment 3

Fig. 5 has described to carry out the device that the contact lithograph method is adopted at 193nm.It comprises 193nmLambda-Physik (Ft.Lauderdale, FL) Optex ArF excimer laser light source, D200 type Scientech (5649 Arapahoe Avenue, Boulder, Colorado 80303) laser power table and immersion fluid reservoir, all these is installed in (46cm) optical table (Newport Corp. of 24 " (61cm) * 18 ", Irvine CA) on, this platform is positioned at Nexus Dry Box (drying box) (the VAC Industries of nitrogen wash, Hawthorne CA) in, drying box has micro oxygen analyzer and moisture probe (VACIndustries).

As shown in Figure 6A, test specimen submergence 1mm in the selected alkane liquid of the present invention of reservoir is dark.Shown in Figure 4 and 5, laser beam was passed distance about 12 before pointing to the target surface vertically downward ".The target surface is the silicon wafer of diameter 100mm * thick 0.5mm, and it is contained on the aluminum frame.This support is installed in orbit, so the sample assembly can move horizontally.On the light path shown in manual shutter places.Shown Scientech power meter is used to measure the total exposure energy of per unit area.Monitor common every cm ²0.2 behind the stable energy of millijoule, the sample holder slip is put in place.

Use has glass syringe (the Popper ﹠amp of Luer-Lock chromium pin; Sons inc., New Hyde Park NY) immersion fluid is assigned in the reservoir of Fig. 6.This pin have 0.2 micron PTFE film injection filter (Pall Gelman Laboratory, Ann Arbor, MI).

Specimen preparation

The silicon single crystal wafer that adopts following method to prepare the 193nm photoetching process to use (Wafernet, Inc., San Jose CA, diameter 100mm * thick 0.5mm, its mirror polish, and native oxide layer is arranged), thick approximately 2nm.This silicon wafer is coated with one deck HMDS (HMDS) in YES-3 Vapor-Prime Oven (YieldEngineering Company, San Jose CA) (Arch Chem.Ind, Norwalk CT), are used as the photoresist adhesion promoter.

(Brewer Science Inc. DerbyEngland), uses the photoresist polymkeric substance to carry out spin coating to adopt CEE 100CB type spinner/electric furnace.This photoresist be shown in following structure 1 1) tetrafluoroethene (TFE), 2) norborene fluorine alcohol (NBFOH) and 3) trimer of tert-butyl acrylate (t-BAc).

As people such as A.E.Feiring, " in the 157nm semiconductor is made; the design of very transparent fluoropolymer resist ", " fluorine chemistry magazine " (Journal of FluorineChemistry), 122,11-16, (2003) described method, use peroxy dicarbonate initiating agent and hydrogen fluorocarbon solvent, adopt the free radical solution polymerization method to prepare this polymkeric substance.The composition of this photoresist polymerization is 33%TFE, 43%NBFOH and 24%t-BA.The photoresist spin coating solution of preparation contains 15 weight % and is dissolved in photoresist polymkeric substance in the 2-heptanone solvent, other 2 weight % are used as the tetrabutyl ammonium lactate (TBALac) that contrast strengthens alkalinity additive as the perfluoro butyl sulfonic acid triphenyl sulfonium salt and the 0.2 weight % of light acid propellant (PAG).This percentage by weight is in total material weight, comprising the spin coating weight of solvent.This resist prescription and disposal route details are referring to people such as M.K.Crawford, " at the photolithographic individual layer fluoropolymer of the 157nm of 157nm exposure wavelength resist ", " resist technology and processing progress " (Resist Technology and Processing), XVIII, SPIEVol.5039, (2003), and people such as A.E.Feiring, the book of quoting previously.

By 0.2 micron teflon injection filter, the photoresist agent solution that about 1ml is so prepared is assigned on the wafer that is coated with HMDS in advance, with 2500rpm spin coating 60 seconds, this resist carried out back baking (PAB) 60 seconds at 150 ℃ to this wafer then in air.The visual examination light actuating resisting corrosion film adopts FilMetrics film thickness instrument (FilmetricsInc., San Diego CA) to measure the thickness of each film.

With 1ml Teflon ^TMAF is assigned on the wafer of painting photoresist, and this wafer was with 2500rpm rotation 1 minute.Then, sample transfer in the VAC drying box, and is put on the sample holder.

Use SPI copper TEM grid (SPI Inc.West Chester PA), diameter 3mm * 50 orders, 500 microns of side direction periodicities, 100 microns of live widths allow its grid be passed in entire wafer on the light beam exposure light path end-to-end, form the contact mask.Use has the glass syringe of 0.2 micron filter, about 20 milliliters of alkane immersion fluids of the present invention are assigned on the silicon wafer of whole diameter 100mm external coating/photoresist/precoating HMDS, the wafer of painting photoresist is immersed in the fluid the about 1mm of its degree of depth.

Allow this wafer along the slide rail that is installed on the optical table, with 1/2cm increment physical transfer in exposure region, thereby a series of 1/2cm are provided the cumulative dosage of band, carry out sequential exposure.After the exposure, siphon away alkane immersion fluid of the present invention, remove the contact mask.Then, with the wafer transfer of exposure outside the VAC drying box, on CEE 100CB type electric furnace, the exposure back 135 ℃ with air under toasted 60 seconds.Then, the FC-75 solvent is assigned to upper wafer surface, allows this wafer in air, rotate 60 seconds again, remove external coating from this wafer by spin coating cleaning action on CEE 100CB type spinner with 2500rpm.Re-use ShipleyLDD-26W developer (Shipley Company, L.L.C., Marlborough MA), under the air of room temperature, be immersed in the developer 60 seconds, make the development of photoresist of exposure like this.Then sample is immersed in 10-15 second in deionization (D.I.) water, from water-bath, takes out,, dry up with nitrogen with the rinsing of D.I. water spray.

By visual and test under microscope dry sample, can determine that contact print dosage E1 does, it means is not having to form the needed lowest exposure energy of image under the situation of immersion liquid; Can also determine that contact print dosage E1 is wet, it means and form the needed lowest exposure energy of image under the situation of not specifying immersion fluid.

Embodiment 3A

The thickness of describing the photoresist layer of preparation as the front is 270nm.This photoresist layer is coated with external coating as described previously.At FLUORINERT ^TMMake 4.1 weight %Teflon among the FC-75 ^TMAF 1601 chemical combination prepare external coating solution.Zhi Bei external coating thickness is 70nm like this.Embodiment 1B cyclohexane give with absorptivity 4.78/cm is that former state is used as immersion liquid.Recording E1 is 4mJ/cm ²At this dosage, as shown in figure 12, copper TEM comb mesh pattern is clearly transferred on the silicon wafer.

Embodiment 3B

Repeat the step of embodiment 3A, but in this case, immersion fluid is except the purity ring hexane of embodiment 1C, and its available light absorptivity 0.14/cm characterizes.The layer thickness of photoresist is 260nm.External coating thickness is 70nm.E1 is 1mJ/cm ²At this dosage, as shown in figure 13, copper TEM comb mesh pattern is clearly transferred on the silicon wafer.Absorptivity reduces by 97%, and E1 reduces by 75%.

Embodiment 3C

Repeat the step of embodiment 3A, but immersion fluid is except the primary sample decahydronaphthalenes (decalin), its available light absorptivity 2.78/cm characterizes, and this external coating is that aforesaid poly-(hexafluoropropylene and the tetrafluoroethene) that is merged at 60: 40 with weight ratio respectively by about 5 weight % is at FLUORINERT ^TMFormulations prepared from solutions in the FC-75 solvent.The thickness of photoresist layer is 260nm.The thickness of external coating is 100nm.E1 is 1.6mJ/cm ²As shown in figure 14, at this dosage, copper TEM comb mesh pattern is clearly transferred on the silicon wafer.

Embodiment 3D

Repeat the step of embodiment 3C, but immersion fluid is except the decahydronaphthalenes (decalin), it is to utilize the step of embodiment 5B to handle, and uses absorptivity 0.45cm ^-1Characterize.The thickness of this photoresist layer is 260nm.The thickness of external coating is 100nm.E1 is 0.8mJ/cm ², as shown in figure 15, at this dosage, copper TEM comb mesh pattern is clearly transferred on the silicon wafer.Absorptivity reduces by 84%, and E1 reduces by 50%.

The comparative example 2

As embodiment 3A, implement identical step, but present embodiment does not use except any immersion fluid and the external coating.The thickness of photoresist layer is 246nm.E1 is 1.2mJ/cm ², be in photoresist, to realize forming knowing that image is needed.The copper TEM comb mesh pattern of transferring on the wafer is shown on Figure 16.

Embodiment 4

A. according to the previously described relative transmission beam method of this paper, tested the absorptivity of primary sample cyclooctane (Fluka catalog number (Cat.No.) 29598, purity 〉=99.5% that adopts GC to obtain, boiling point 150-152 ℃), recording is 1.84cm under 193nm ^-1

B., about 2ml dry silica gel as providing among the embodiment 1 is provided in the 5ml primary sample cyclooctane.This silica gel in glove box at N ₂Under filter after, adopting relative transmission beam method to record processing cyclooctane like this is 1.13cm in the absorptivity of 193nm ^-1

Embodiment 5

A. according to relative transmission beam method, use multiple optical path length to measure the absorptivity of primary sample decahydronaphthalenes under nitrogen, the primary sample decahydronaphthalenes is the potpourri (Fluka catalog number (Cat.No.) 30490 adopts GC to record purity 〉=98%) of cis and trans-isomer.The primary sample decahydronaphthalenes is 2.78cm in the absorptivity of 193nm ^-1

B. in 500ml primary sample decahydronaphthalenes, add the about 350ml dry silica gel that provides as embodiment 1.This silica gel in glove box at N ₂Under filter after, the decahydronaphthalenes that adopts relative transmission beam method to record processing like this is 0.17cm in the absorptivity of 193nm ^-1

C. adopt minimum deviation method previously discussed to measure the refractive index of decahydronaphthalenes.22 ℃ of refractive indexes in 193nm is 1.641, is 1.546 at 248nm, is 1.634 31 ℃ of refractive indexes in 193nm, is 1.540 at 248nm.

Embodiment 6

A. adopt relative transmission beam method under nitrogen, to measure the absorptivity of primary sample cis decahydronaphthalenes (Fluka catalog number (Cat.No.) 30500, purity 〉=98% that adopts GC to record).Correction absorptivity at 193nm is＞300cm ^-1

B. silica gel powder (Fluka, catalog number (Cat.No.) 60738, granularity 0.035-0.070mm, 220-440 order, ASTM) under 500 ℃ of air dry 2 hours.From be equipped with 25ml so first post of dry silica gel powder wash-out go out 50ml cis decahydronaphthalenes, then from second post wash-out of 15ml silica gel powder is housed.The cis decahydronaphthalenes that adopts relative transmission beam method to record processing like this is 0.75cm in the absorptivity of 193nm ^-1

C. adopt minimum deviation method previously discussed to measure the refractive index of cis decahydronaphthalenes.22 ℃ of refractive indexes in 193nm is 1.656, is 1.560 at 248nm, is 1.649 30 ℃ of refractive indexes in 193nm, is 1.555 at 248nm.

Embodiment 7

Adopt Varian Cary 5UV/vis/NIR twin-beam spectrometer, follow the step of embodiment 6, measured the absorptivity of the trans decahydronaphthalenes of primary sample (Fluka catalog number (Cat.No.) 30510, purity 〉=98% that adopts GC to record).

B. the trans decahydronaphthalenes of wash-out 25ml from the post that 12ml embodiment 6 dry silica gel powder are housed.Adopting relative transmission beam method to record its absorptivity is 0.46cm at 193nm ^-1

C. adopt minimum deviation method previously discussed to measure the refractive index of trans decahydronaphthalenes.22 ℃ of refractive indexes in 193nm is 1.643, is 1.548 at 248nm.31 ℃ of refractive indexes in 193nm is 1.636.

Embodiment 8

A. adopt relative transmission beam method described herein, record primary sample 1,1 '-dicyclohexyl (Fluka catalogue #14356, the purity 99.0% that adopts GC to record) is 31.40cm in the absorptivity of 193nm ^-1

B. dry silica gel that about 10ml such as embodiment 1 provide and 20ml primary sample dicyclohexyl merge.This silica gel in glove box at N ₂Under filter after, adopting relative transmission beam method to record absorptivity is 0.31cm at 193nm ^-1

Embodiment 9

A. at room temperature, pack in the 100g and outer 5-vinyl-2-norborene (Aldrich 14,867-9,95%), 150ml methyl alcohol (Burdick ﹠amp toward the 400ml autoclave; Jackson, HPLC level) and the potpourri of activated carbon-carried palladium (1g, Alfa product powder contains 10%Pd).Close and seal this autoclave, at room temperature under the 50psig hydrogen-pressure, stirred 1 hour then.At room temperature, in the second hour, Hydrogen Vapor Pressure is increased to 200psig gradually, then in 2 hours, is increased to 400psig, in 1 hour, be increased to 620psig at 150 ℃ again at 100 ℃.Behind the cool to room temperature, this reaction mixture filters, and removes catalyzer.This filtrate is divided into two-layer.Bottom uses 50ml equal portions water washing twice after separating, with the Na of anhydrous particle shape ₂SO ₄(EMScience) drying.Remove Na ₂SO ₄After, obtain the 79g product liquid, be referred to as product A here.Allow the top layer reaction filtrate in two-layer mix, so formed two-layer liquid again with 500ml water.Separate for example top layer of this generation,, use Na with 20ml equal portions water washing twice ₂SO ₄Dry.Remove Na ₂SO ₄After, obtain the 19g product liquid, be referred to as product B here.Discovery product A and product B are formed by the 2-ethyl norcamphane more than 99%.Merging productive rate is 96%.In product A and product B, all found micro-olefin contaminants.Two samples at room temperature use bromine (0.12g, Aldrich, more senior reagent) to handle a night.Use NaHSO ₃Excessive bromine is removed in (moisture) and water washing.Use Na ₂SO ₄After the drying, these samples merge, decompression distillation.(106 ℃ of boiling points/185mmHg) absorptivity at 193nm is 61.4cm in the middle distillate of distillation ^-1This cut is transferred to clean bottle (VWR, VWR  TraceClean ^TMBottle has the Teflon liner seal) in, nitrogen purge used.In drying box, the activated silica gel that provides toward this bottle interpolation such as embodiment 1 (reducible liquid volume 1/3).Cover bottle, shook about 30 seconds, at room temperature stopped several days then.This liquid adopts the Acrodisc  CR25mm injection filter (Pall Life Science) of band 200nm PTFE film to filter.Filter liquide is 1.83cm in the absorptivity of 193nm ^-1After carrying out for the second time such processing, liquid is 0.98cm in the absorptivity of 193nm ^-1

B. as embodiment 9-A, another batch 2-ethyl norcamphane is with silica gel treatment three times.The absorptivity that obtains at 193nm is 0.81cm ^-1Adopt minimum deviation method previously discussed to measure the refractive index of processing 2-ethyl norcamphane like this.22 ℃ of refractive indexes in 193nm is 1.613.31 ℃ of refractive indexes in 193nm is 1.607, is 1.525 at 248nm.

Embodiment 10

A. (absorptivity that records at 193nm is 2.24cm for TCI-EP catalog number (Cat.No.) 00138, absorptivity 98+%) to have tested primary sample n-octyl group cyclohexane according to above-mentioned relative transmission beam method ^-1

B. silica gel (Aldrich catalog number (Cat.No.) 24,982-3, class 3,8 orders) was air and 500 ℃ dry 2 hours down.Activated charcoal (Calgon charcoal Corporation, Type C PG LF 12 * 40) was nitrogen and 200 ℃ dry 2 hours down.In bag glove, the so dry silica gel of following about 4ml of N2 and 3ml for example this dry activated carbon be added to and be contained in VWR TraceClean ^TM15ml primary sample n-octyl group cyclohexane in the bottle.At room temperature, n-octyl group cyclohexane, activated charcoal and silica-gel mixture are at the VWR of sealing ^TMTraceClean ^TMPlaced 6 days in the bottle.This bottle is transferred in the nitrogen glove box.Pour out several milliliters of n-octyl group cyclohexanes, silicon dioxide and charcoal are poured into 0.45 micron Luer-Lok of configuration ^TMIn the 15ml BD syringe of PTFE filtrator.Filtrate is collected in clean VWR TraceClean ^TMIn the bottle.Transfer in the Harrick pond with the filtrate that clean 1ml glass syringe will about 0.5ml so obtains.The n-octyl group cyclohexane that adopts the previously described relative transmission beam method of this paper to record processing like this is 1.78cm in the absorptivity of 193nm ^-1

C. silica gel (Aldrich catalog number (Cat.No.) 24,982-3, class 3,8 orders) was air and 500 ℃ dry 2 hours down.In bag glove, the past VWR TraceClean that is contained under blanket of nitrogen ^TM5ml primary sample n-octyl group cyclohexane in the bottle adds this silicon dioxide of about 2ml.From bag glove, take out this bottle, shake, be allowed to condition in the laboratory and place a night.Be put back into bottle in the bag glove the next morning, and silicon dioxide filters with 0.45 μ glass microfiber injection filter (Whatman  Autovial  #AV125UGMF), and filtrate is collected in new VWR TraceClean ^TMIn the bottle.This bottle is taken another laboratory, place new nitrogen bag glove, transferring to 0.5cm again has in the absorption cell of quartz window.Adopt the step of embodiment 4, the absorptivity of n-octyl group cyclohexane of having used Varian Cary5UV/vis/NIR twin-beam spectrophotometer.Correction absorptivity at 193nm is 2.0.

Embodiment 11: decane

A. (anhydrous, 99+% uses Sure/Seal under nitrogen for Aldrich catalog number (Cat.No.) 45,711-6 to adopt the previously described VUV Vase of this paper absorptivity method to measure the primary sample decane ^TMThe bottle packing) absorptivity, recording at 193nm is 3.43cm ^-1

B. silica gel (Aldrich catalog number (Cat.No.) 24,982-3, class 3,8 orders) 500 ℃ with air under dry 2 hours.In the nitrogen bag glove, in 40ml primary sample decane, add this silica gel of 28ml.In glove box, at N ₂Under remove by filter silica gel after, adopt the previously described method of this paper, use VUV Vase absorptivity, recording processing decane like this is 0.54cm in the absorptivity of 193nm ^-1

C. adopt minimum deviation method previously discussed to measure the decane refractive index.22 ℃ of refractive indexes in 193nm is 1.549, is 1.476 at 248nm.

D. use the mode of operation of 1cm absorption cell according to embodiment 4, adopt Varian Cary5UV/vis/NIR twin-beam spectrometer, measured the absorptivity of 10ml primary sample decane.Correction absorptivity at 193nm is 3.12cm ^-1

E. in bag glove, will about 1ml under blanket of nitrogen such as embodiment 1 dried silica and the 10ml primary sample n-decane that provide merge.Under nitrogen, use 0.45 μ glass microfiber injection filter (Whatman  Autovial  #AV125UGMF) to remove by filter silicon dioxide.According to the mode of operation of embodiment 4 use 1cm absorption cells, adopt Varian Cary 5UV/vis/NIR twin-beam spectrometer.Correction absorptivity at 193nm is 0.67cm ^-1

F. according to the 11D method, but use except about 3ml dry silica gel.Correction absorptivity at 193nm is 0.61cm ^-1

G. according to the 11D method, but use except about 5ml dry silica gel.Correction absorptivity at 193nm is 0.46cm ^-1

H. according to the 11D method, but use except about 7ml dry silica gel.Correction absorptivity at 193nm is 0.29cm ^-1

I. according to the 11D method, but use except about 9ml dry silica gel.Correction absorptivity at 193nm is 0.29cm ^-1

Embodiment 12:

A. according to the previously described relative transmission beam method of this paper, recording primary sample dodecane (Fluka catalog number (Cat.No.) 44010, purity＞99.8% that adopts GC to record) is 0.70cm in the absorptivity of 193nm ^-1

B. add the dry silica gel that about 2ml such as embodiment 1 provide in the 5ml primary sample dodecane.In glove box, at N ₂Under remove by filter silica gel after, adopt relative transmission beam method, the dodecane that records processing like this is 0.22cm in the absorptivity of 193nm ^-1

C. adopt minimum deviation method previously discussed to measure the refractive index of dodecane.22 ℃ of refractive indexes in 193nm is 1.564, is 1.489 at 248nm.30 ℃ of refractive indexes in 193nm is 1.558, is 1.484 at 248nm.

Embodiment 13:

A. adopt the previously described relative transmission beam method of this paper, recording 5ml primary sample hexadecane (Fluka catalog number (Cat.No.) 52209, purity 〉=99.8% that adopts GC to record) is 6.15cm in the absorptivity of 193nm ^-1

B. add the dry silica gel that about 15ml such as embodiment 1 provide in the 20ml primary sample hexadecane.In glove box, at N ₂Under remove by filter silica gel after, the hexadecane that adopts relative transmission beam method to record processing like this is 0.72cm in the absorptivity of 193nm ^-1

C. adopt minimum deviation method previously discussed to measure the refractive index of hexadecane.22 ℃ of refractive indexes in 193nm is 1.581, is 1.504 at 248nm.32 ℃ of refractive indexes in 193nm is 1.573.

Embodiment 14:

A. according to the previously described relative transmission beam method of this paper, recording the primary sample tetradecane (Fluka catalog number (Cat.No.) 87139, purity 〉=99.5% that adopts GC to record) is 2.06cm in the absorptivity of 193nm ^-1

B. in the fresh sample bottle, the dry silica gel that the 5ml primary sample tetradecane and 2ml such as embodiment 1 are provided merges.In glove box, at N ₂Under remove by filter silica gel after, the tetradecane that adopts relative transmission beam method to record processing like this is 1.00cm in the absorptivity of 193nm ^-1

Embodiment 15:

A. adopt relative transmission beam method, recording primary sample 2-methylpentane (Aldrich catalogue #M6,580-7, purity 99+%, 62 ℃ of boiling points) is 43.33cm in the absorptivity of 193nm ^-1

B. in bag glove, at N ₂Down will about 12ml such as embodiment 1 dry silica gel and the 25ml primary sample 2-methylpentane that provide merge.In glove box, this silica gel is at N ₂Under filter after, adopting relative transmission beam method to record processing 2-methylpentane like this is 0.16cm in the absorptivity of 193nm ^-1

C. in bag glove, under N2, add dry silica gel and 4ml 3A molecular sieve (EMD catalogue #MX1583D-1,8-12 order pearl) that about 8ml such as embodiment 1 provide in the 25ml primary sample 2-methylpentane, this molecular sieve is air and 500 ℃ times dryings 2 hours.In glove box, at N ₂Under remove by filter silica gel after, the 2-methylpentane that adopts relative transmission beam method to record processing like this is 0.21cm in the absorptivity of 193nm ^-1

D. in bag glove, under N2, respectively add the dry silica gel that 4ml such as embodiment 1 provide, dry molecular sieves and 4ml activated charcoal (the Calgon charcoal Corporation of embodiment 13C in the 25ml primary sample 2-methylpentane, CPG LF 12 * 40 classes), activated charcoal is under 200 ℃ of nitrogen dry 2 hours.In glove box, at N ₂Under remove by filter silica gel, molecular sieve and charcoal after, the 2-methylpentane that adopts relative transmission beam method to record processing like this is 0.05cm in the absorptivity of 193nm ^-1

Adopt minimum deviation method previously discussed to measure the refractive index of 2-methylpentane.22 ℃ of refractive indexes in 193nm is 1.495, is 1.429 at 248nm.

E. having adopted Varian Cary 5 spectrophotometer is 0.724cm as the strict absorptivity of handling sample of embodiment 13B ^-1

Embodiment 16: the 3-methylpentane

A. (99+%) absorptivity at 193nm is 43.33cm for Aldrich catalog number (Cat.No.) M6,600-5 to adopt relative transmission beam method to record primary sample 3-methylpentane ^-1

B. in glove box, under N2, add the charcoal of 8ml silica gel and 7ml embodiment 13 D in the 30ml primary sample 3-methylpentane.In glove box, at N ₂Under remove by filter silica gel and charcoal after, the 3-methylpentane that adopts relative transmission beam method to record processing like this is 0.44cm in the absorptivity of 193nm ^-1

Embodiment 17:2, the 3-dimethylbutane

A. in bag glove, will about 2ml under blanket of nitrogen such as embodiment 1 dry silica gel and the 5ml 2 that provide, (Aldrich catalog number (Cat.No.) D15,160-2 98+%) merge the 3-dimethylbutane.In bag glove, under nitrogen, filter silicon dioxide with 0.45 μ glass microfiber injection filter (Whatman  Autovial  #AV125UGMF).Adopted Varian Cary 5UV/vis/NIR twin-beam spectrophotometer 2, the absorptivity of 3-dimethylbutane.Proofreading and correct absorptivity is 1.85cm at 193nm ^-1

B. adopt the previously described relative transmission beam method of this paper, measure 2 of primary sample form, the absorptivity of 3-dimethylbutane, the absorptivity that records at 193nm is 6.58cm ^-1

C. in bag glove, under N2,, add the charcoal of 8ml silica gel and 7ml embodiment 13 D in the 3-dimethylbutane toward 30ml primary sample 2.In bag glove, at N ₂Under remove by filter silica gel and charcoal after, adopt relative transmission beam method to record 2 of processing like this, the 3-dimethylbutane is 0.65cm in the absorptivity of 193nm ^-1

Embodiment 18:

A. adopt relative transmission beam method to record primary sample 2,2-dimethylbutane (Fluka catalogue #39740, purity 〉=99% that adopts GC to record) is 2.15cm in the absorptivity of 193nm ^-1

B. toward 20ml primary sample 2, add each about 5ml silica gel in the 2-dimethylbutane and as the 3A molecular sieve of embodiment 13D.In glove box, at N ₂Under remove by filter silica gel and the sieve after, adopt relative transmission beam method to record 2 of processing like this, the 2-dimethylbutane is 0.46cm in the absorptivity of 193nm ^-1

C. toward 20ml primary sample 2, add the dry silica gel that about 10ml such as embodiment 1 provide in the 2-dimethylbutane.In glove box, at N ₂Under remove by filter silica gel after, adopt relative transmission beam method to record 2 of processing like this, the 2-dimethylbutane is 0.33cm in the absorptivity of 193nm ^-1

D. in bag glove, under N2 toward 20ml primary sample 2, the charcoal that adds each about 5ml dried silica and prepare in the 2-dimethylbutane as embodiment 13D.In glove box, at N ₂Under remove by filter silica gel and charcoal after, adopt relative transmission beam method to record 2 of processing like this, the 2-dimethylbutane is 0.23cm in the absorptivity of 193nm ^-1

Adopt minimum deviation method previously discussed to measure 2, the refractive index of 2-dimethylbutane.30 ℃ of refractive indexes in 193nm is 1.481, is 1.415 at 248nm.This is corresponding to effective photoetching process wavelength 130.6nm of 193nm light, effective photoetching process wavelength 175.3nm of 248nm light.

E. in bag glove, under blanket of nitrogen,, add the dry silica gel that about 2ml such as embodiment 1 provide in the 2-dimethylbutane toward 5ml primary sample n-2.In bag glove, under nitrogen, remove by filter silicon dioxide with 0.45 μ glass microfiber injection filter (Whatman  Autovial  #AV125UGMF).Varian Cary 5 UV/vis/NIR twin-beam spectrophotometer have been adopted 2, the absorptivity of 2-dimethylbutane.Proofreading and correct absorptivity is 0.424 at 193nm.

Embodiment 19:

A. (purity＞99+%) is at absorptivity＞100cm of 193nm for Aldrich catalog number (Cat.No.) C10,940-1 to adopt relative transmission beam method to record the primary sample cyclooctane ^-1

B. under 500 ℃ of air, and silica white (Fluka, catalog number (Cat.No.) 60738, granularity 0.035-0.070mm, the 220-440 order ASTM) carried out drying 2 hours.Go out the 100ml cyclooctane by the post wash-out that 50ml front dry silica gel powder is housed, then by second post at the new dry silica white of 30ml end is housed.Absorptivity/the cm that uses relative transmission beam method to record at 193nm is 0.47cm ^-1

Adopt minimum deviation method previously discussed to measure the refractive index of cyclooctane.22 ℃ of refractive indexes in 193nm is 1.615, is 1.532 at 248nm.30 ℃ of refractive indexes in 193nm is 1.606, is 1.525 at 248nm.

Embodiment 20:

A. adopting relative transmission beam method to record primary sample decane (Fluka catalog number (Cat.No.) 30540, the purity 99.8% that adopts GC to record) is 6.01 in the absorptivity of 193nm.

B. in the nitrogen bag glove, dry silica gel and 10ml primary sample decane that about 5ml such as embodiment 1 are provided merge.In glove box, at N ₂Under remove by filter silica gel after, the decane that adopts relative transmission beam method to record processing like this is 0.56cm in the absorptivity of 193nm ^-1

Embodiment 21: cycloheptane

A. buy cycloheptane (catalogue #28810, purity 〉=97% that adopts GC to record), boiling point 116-118 ℃ from Fluka.The absorptivity of cycloheptane that adopted Varian Cary 5 UV/vis/NIR twin-beam spectrophotometer.The empty absorption cell of 100 μ m that will have quartz window is inserted between electron beam and the zero base line by the 185-350nm generation.In being full of the bag glove of nitrogen, take out the sample beam absorption cell from the Cary5 spectrometer, fill cycloheptane.Absorption cell is put back on Cary 5 spectrometers, measures the absorptivity of 185-350nm.Deviation (here decane is non-absorbent) at 350nm place and zero base line is added on the absorptivity that 193nm measures, as final correction.Correction absorptivity at 193nm is＞390cm ^-1

B. under air and 500 ℃, and the dring silicon rubber powder (Fluka, catalog number (Cat.No.) 60738, granularity 0.035-0.070mm, the 220-440 order, ASTM).Obtain the 100ml cyclopentane from the post wash-out that 50ml front dring silicon rubber powder is housed.Absorptivity at 193nm is 49.89cm ^-1

C. behind second silicagel column wash-out, adopting Cary 5 spectrometers to record cycloheptane is 0.95cm in the absorptivity of 193nm ^-1

D. under air and 500 ℃, dry 2 hours of silica gel (Aldrich catalog number (Cat.No.) 24,982-3, class 3,8 orders).Add this silica gel of about 7.5ml toward the above-mentioned cycloheptane of 10ml.In glove box, under N2, remove by filter silica gel after, the cycloheptane that adopts relative transmission beam method to record processing like this is 0.75cm in the absorptivity of 193nm ^-1

Adopt minimum deviation method previously discussed to measure the refractive index of cycloheptane.22 ℃ of refractive indexes in 193nm is 1.598, is 1.517 at 248nm.30 ℃ of refractive indexes in 193nm is 1.591, is 1.511 at 248nm.

Embodiment 22:

According to people such as Plate, " general chemistry magazine " (Zhurnal Obshchei Khimii), 30,3945-53,1960 described literature methods have prepared the octahydro indenes.The octahydro indenes (20g) and the concentrated sulphuric acid (15g) at room temperature stirred 2 days.The top layer that separates this reaction mixture with NaHCO3 (moisture), water and NaCl (saturated) washing, is used the Na2SO4 drying, distills then to obtain liquid (14.2g, 35 ℃ of boiling points/2mmHg).In drying box, this liquid is added at VWRTraceClean ^TMIn interior about 1/3 (volume) silica gel of bottle.[dry 2 hours of vacuum and 500 ℃ of following silica gel (Aldrich catalog number (Cat.No.) 24,982-3, class 3,8 orders)].Cover bottle, shook about 30 seconds.At room temperature placed several days then.This liquid filters with the Acrodisc  CR 25mm injection filter that has 200nm PTFE film (Pall Life Science).Adopting the above-mentioned relative transmission beam method of this paper to record filter liquide is 0.89cm in the absorptivity of 193nm ^-1

Embodiment 23:

From Dixie Chemical Company, Inc., Houston, TX buy outer-tetrahydro-dicyclopentadiene roller of one 54 gallons.Under nitrogen, small amount of sample is transferred to VWRTraceClean ^TMIn the bottle.Adopt Varian Cary 5 its transparencies of UV/vis/NIR twin-beam spectrophotometer, the transparency that records at 193nm is 16cm ^-1

1 inch of diameter, high 12 inches glass column have the top be subjected to the positive pressure of nitrogen protection～the 200ml glass bead, and be equipped with whole Teflon ^TMDo not have oily joint, allow this chromatographic column with have a 1/8 " O.D.Teflon ^TMThe nitrogen bag glove of pipe links to each other.Glass wool pulvinulus Vertrel ^TMNitrogen drying is used in the rinsing of XF solvent, then it is seated in the glass column bottom, prevents that bottom piston is blocked afterwards.

Under moving air and 500 ℃, in the Hastelloy pipe, about 80ml ICN aluminium oxide NAkt.1, catalog number (Cat.No.) 02084 heated 2 hours.Stop airflow, sealed tube is cooled near room temperature again.Add aluminium oxide toward this chromatographic column then, slowly clean this post from the bottom with nitrogen simultaneously.

Outside the about 240ml Dixie Chemicalr of chromatographic column interpolation that aluminium oxide is housed-tetrahydro-dicyclopentadiene.This post cleans half an hour approximately with N2 stream slowly, and this N2 stream passes aluminium oxide and outer-tetrahydro-dicyclopentadiene upwards drops down at the bottom of the post.

When nitrogen purge is finished, outside in several hours, allowing-tetrahydro-dicyclopentadiene comes out from the slow wash-out of this post, passes Teflon ^TMPipe is directly delivered to the dry VWR TraceClean of heating gun in being full of the nitrogen bag glove ^TMPipe.Cutting continuously, each about 20ml (volume).Under nitrogen, in Varian Cary 5 UV/vis/NIR twin-beam spectrometers, measure the absorptivity of each cutting then with the 1cm absorption cell.Absorptivity result comes together in the following table.

Cutting #	Elution volume	?A/cm@193nm
			1	?0-20ml	?0.16
2	?20-40ml	?0.14
			3	?40-60ml	?0.16
4	?60-80ml	?0.15
			5	?80-100ml	?0.14
6	?100-120ml	?0.17
			7	?120-140ml	?0.26
8	?140-160ml	?0.41
			9	?160-180ml	?0.41

Adopt this paper minimum deviation method previously discussed measured similar preparation outer-refractive index of tetrahydro-dicyclopentadiene sample is 1.660 at 23 ℃, is 1.655 at 32 ℃, the absorptivity/cm that adopts relative transmission beam method to be determined at 193nm is 0.42/cm.

Embodiment 24

With the Ocean Optics FOXY probe of estimating resolution 2ppm be immersed in the liquid cyclohexane sample surfaces below, measured dissolved oxygen concentration.In the VUV-Vase spectrometer, adopt relative transmission beam method to measure optical absorptivity at 193nm, the absorptivity that two different Herrick ponds thickness (1.45mm and 6.0mm) are measured averages.

In the nitrogen drying case, the about 100ml that stores under nitrogen and silica gel purity ring hexane is by 0.2 μ m Teflon ^TMFiltrator is expelled in the 125ml EaglePicher bottle.This 125ml EaglePicher bottle has a silicon/Teflon ^TMMembrane cover, inside have a coating Teflon ^TMStirring rod.The dissolved oxygen concentration of having found to prepare like this cyclohexane filtrate is 1.1ppmw.Optical absorptivity is 0.12cm ^-1

Take off membrane cover, allow the content in the bottle under agitation be exposed to air following 15 minutes.Cover bottle with barrier film again, allow and leave air in the bottle.The dissolved oxygen concentration that records the saturation of the air cyclohexane the next morning is 86ppmw, and optical absorptivity is 1.88cm ^-1

Allowing nitrogen tube pass membrane cover through syringe needle arrives below the cyclohexane surface.Speed with 0.04 liter of per minute made nitrogen bubble 210 seconds by cyclohexane, discharged excessive nitrogen by second syringe needle that penetrates membrane cover.The dissolved oxygen concentration 24.1ppmw of bubbling cyclohexane like this, optical absorptivity is 0.59/cm.

Made the cyclohexane bubbling for the second time 240 seconds with nitrogen.Behind the bubbling, the dissolved oxygen concentration of twice bubbling cyclohexane is 8.0ppmw for the second time, and optical absorptivity is 0.20/cm.

Cyclohexane is bubbling 38 minutes for the third time.Behind the bubbling, the dissolved oxygen concentration of cyclohexane is 0ppmw (promptly is lower than the estimation detectability and limits about 2 ppm) for the third time, and optical absorptivity is 0.27/cm.

Dissolving O2 concentration is to the influence of cyclohexane absorptivity

Sample	Abs./cm @193nm	O2?Conc. ppmw+/-2ppm	Explain
				A	0.12	1.1	The purifying initial sample
B	1.88	86.0	Be exposed to room air
				C	0.59	24.1	Part N2 bubbling, 3.5min
D	0.20	8.0	Part N2 bubbling, 4min
				E	0.27	0	Complete bubbling, 38min

Data in the last table show that the oxygen that every ppm is dissolved in the cyclohexane will improve cyclohexane in about 0.02 unit of the mensuration absorptivity of 193nm.Therefore, the requirement of measuring precision (+/-0.02) and can accepting transparency liquid for our A/cm limit (A/cm＜1, preferably＜0.1) the two, the influence of≤1ppm dissolved oxygen DO is little as to be almost equal to zero.According to Henry's law, should adopt heavy dose of oxygen in the nitrogen (＞2300ppm) surpass the cyclohexane sample, force that dissolved oxygen content surpasses 1ppmw in the cyclohexane.Adopt our packing to be easy to reach, and remain on gas phase level＜2300ppm oxygen on the cyclohexane.

Do you why will expect that the oxygen level set is at＜2300ppm? on long terms, the hydrocarbon O of cyclohexane and so on for example ₂Oxidation produces strong 193nm chromophore, and it should reach＜1ppm, just keeps our absorptivity standard.We think that our packing can protect this fluid for a long time.The packing method that designs us reaches and keeps the oxygen horizontal properties or the gas cylinder nitrogen (cylindernitrogen) of glove box, or is the middle mutually about 2-5ppm oxygen of nitrogen on the cyclohexane.According to Henry's law, when the nitrogen that contains 5ppm oxygen was arranged on the cyclohexane, dissolved oxygen concentration should be about 0.2ppb (parts per billion) in the cyclohexane.Keep the following dissolved oxygen DO of 0.2ppb or 0.2ppb in the cyclohexane, the reaction that can eliminate dissolved oxygen DO and cyclohexane effectively is along with the danger (suppose a container, wherein the volume of nitrogen can not substantially exceed the volume of cyclohexane) of appreciable impact time lapse at the A/cm of 193nm.

Claims (44)

1. composition, it is made up of liquid alkane basically, and the oxygen concentration of this liquid alkane is less than 2ppm, is 1cm in the absorptivity of 193nm wavelength ^-1Or 1cm ^-1Below.

2. composition according to claim 1, wherein this liquid alkane is selected from: cyclopentane, cyclohexane, cycloheptane, cyclooctane, decane, decahydronaphthalenes racemic compound, cis decahydronaphthalenes, trans decahydronaphthalenes, outer-tetrahydro-dicyclopentadiene, 1,1 '-bis cyclohexane, 2-ethyl norcamphane, n-octyl group-cyclohexane, dodecane, the tetradecane, hexadecane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, octahydro indenes and composition thereof.

3. composition according to claim 1, wherein the refractive index of this liquid alkane is 1.6-1.7.

4. composition according to claim 3, wherein this liquid alkane is selected from: cyclopentane, cyclohexane, decahydronaphthalenes racemic compound, cis-decahydronaphthalenes, trans-decahydronaphthalenes, outer-tetrahydro-dicyclopentadiene, 1,1 '-bis cyclohexane and composition thereof.

5. composition according to claim 1, wherein this absorptivity is 0.01-1cm ^-1

6. composition according to claim 5, wherein this absorptivity is 0.01-0.5cm ^-1

7. method, this method comprises provides transmitted wave to be about the light source of the UV radiation of 170-260nm, the target surface is provided, irradiation at least a portion target surface, the UV radiation along a light path from light source is arranged, and at least a portion light path, place liquid alkane and handle, wherein liquid alkane is made up of one or more alkanes of the non-annularity alkane that is selected from side chain or non-side chain or ring-type alkane and its potpourri basically.

8. method according to claim 7, wherein this alkane is selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, decane, decahydronaphthalenes racemic compound, cis-decahydronaphthalenes, trans-decahydronaphthalenes, outer-tetrahydro-dicyclopentadiene, 1,1 '-bis cyclohexane, 2-ethyl norcamphane, n-octyl group-cyclohexane, dodecane, the tetradecane, hexadecane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, octahydro indenes and composition thereof.

9. method according to claim 8, wherein this alkane is 2,3-dimethylbutane racemic compound.

10. method according to claim 7, wherein this liquid is lower than 1cm in the absorptivity of 193nm ^-1

11. method according to claim 10, wherein this absorptivity is 0.01-1cm ^-1

12. method according to claim 10, wherein this absorptivity is 0.01-0.5cm ^-1

13. method according to claim 7, wherein the refractive index of this liquid alkane is 1.6-1.7 in this wavelength coverage.

14. method according to claim 7, wherein this light source is the laser of emission 193nm light.

15. method according to claim 7, wherein this light source is the laser of emission 248nm light.

16. method according to claim 7, wherein the photoresist polymkeric substance is contained on this palladium surface.

17. method according to claim 16, wherein the external coating polymkeric substance is also contained on this palladium surface.

18. method according to claim 7 wherein is immersed in this surface in this liquid alkane.

19. according to claim 7 or the described method of claim 13, wherein this light source is the laser of emission 193nm light, the photoresist polymkeric substance is contained on this surface, and this surface is immersed in this liquid, wherein shines this surperficial light and causes that this surface becomes image exposure.

20. according to claim 7 or the described method of claim 13, wherein this light source is the laser of emission 248nm light, the photoresist polymkeric substance is contained on this surface, and this surface is immersed in this liquid, wherein shines this surperficial light and causes that this surface becomes image exposure.

21. method according to claim 7, this method also comprise from this alkane liquid extraction pollutant.

22. method according to claim 21, wherein this extraction comprises and allows this liquid contact with adsorbent.

23. method according to claim 22, wherein this adsorbent is selected from silica gel, charcoal, molecular sieve, aluminium oxide and composition thereof.

24. also comprising, method according to claim 21, this method handle and remain on the extracting liq that contains in the minimum atmosphere of oxygen.

25. also being included in this liquid, method according to claim 22, this method also to not have the grease fractionation before contacting with this adsorbent.

26. method according to claim 7 after this method also is included in exposure, makes this liquid regeneration in closed loop liquid circulation and refining system, this system comprises one or more adsorbent bed and contains the minimum atmosphere of oxygen.

27. equipment, it comprises the light source of emission wavelength 170-260nm light, surface of handling like this, so that when this light source activates, rayed at least a portion surface by radiative light emitted, and liquid alkane so places between this light source and this surface, so that shines this surperficial at least a portion emission light and propagate by its liquid alkane.

28. equipment according to claim 27, wherein this liquid alkane in the absorptivity of 193nm less than 1cm ^-1

29. equipment according to claim 27, wherein this absorptivity is 0.01-1cm ^-1

30. equipment according to claim 29, wherein this absorptivity is 0.01-0.5cm ^-1

31. equipment according to claim 27, wherein this liquid is at the refractive index 1.6-1.7 of wavelength 170-260nm.

32. equipment according to claim 27, wherein this light source is the laser of emission 193nm light.

33. equipment according to claim 27, wherein this light source is the laser of emission 248nm light.

34. equipment according to claim 27, wherein the photoresist polymkeric substance is contained on this surface.

35. equipment according to claim 34 wherein should also contain the external coating polymkeric substance in the surface.

36. equipment according to claim 27 wherein is immersed in this palladium surface in this liquid alkane.

37. according to claim 27 or the described equipment of claim 31, wherein this light source is the laser of emission 193nm light, the photoresist polymkeric substance is contained on this surface, this surface is immersed in this liquid, and this equipment has the function of finishing this surface one-tenth image exposure.

38. according to claim 27 or the described equipment of claim 31, wherein this light source is the laser of emission 248nm light, the photoresist polymkeric substance is contained on this surface, this surface is immersed in this liquid, and this equipment has the function of finishing this surface one-tenth image exposure.

39. equipment according to claim 35, wherein this external coating is made up of the amorphous fluorinated polymer that dissolves in the fluorated solvent basically.

40. according to the described equipment of claim 39, wherein this amorphous fluorinated polymer comprises the multipolymer that is selected from following monomer preparation by two or more: hexafluoropropylene, tetrafluoroethene, perfluor dimethyl dioxole, perfluorinated methyl ethylene ether, perfluorobuttene base vinethene and perfluoro propyl vinethene, or this polymkeric substance is a perfluorobuttene base vinethene homopolymer.

41. according to the described equipment of claim 40, wherein this multipolymer contains the monomeric unit that the monomeric unit of being derived by tetrafluoroethene and 30-90 mole % are derived by perfluor dimethyl dioxole.

42. equipment according to claim 27, it also comprises and contains the minimum atmosphere of oxygen.

43. equipment according to claim 27, it also comprises closed loop liquid circulation and refining system, and this system comprises one or more adsorbent bed and contains the minimum atmosphere of oxygen.

44. equipment according to claim 27, wherein this alkane is made up of the alkane that one or more are selected from non-annularity alkane, ring-type alkane, side chain alkane, non-side chain alkane and composition thereof basically.

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