FR2782175A1 - RESERVE ELIMINATION METHOD AND DEVICE - Google Patents

Abstract

This invention relates to a resist removal method and to a resist removal device using this method. The resist removal method includes disposing a substrate and forming a resist on the substrate. Next, the substrate is contacted with a resist removing agent comprising an N-alkanol-alkoxy-alkanamide, to remove the resist on the substrate. Alternatively, the substrate is contacted with a resist removal composition which may comprise an N-alkanol-alkoxy-alkanamide with an attack inhibitor, or an alkanolamine and an alkyl alkoxyalkanoate. Since the resist can be removed by a simple process in a short time, and since the resist removing device can have a reduced size, the productivity of a semiconductor device manufacturing facility can be increased.

Description

RESERVE ELIMINATION METHOD AND DEVICE

  Technical Field The present invention relates to a reserve elimination method, a reserve elimination device and a semiconductor device produced by the method. More particularly, the present invention relates to a method and a device for reserve elimination which direct a new elimination material.

  reserve on a reserve on a substrate.

  PRIOR ART The reserve elimination process is a process

  major in the preparation of a semi-

  driver. For example, after various processes for preparing the semiconductor device, for example an etching process (dry or wet) or an ion implantation process, a resist pattern, which

  is used as a mask on a semi-substrate

  conductor, must be eliminated. Also, if the reserve pattern is misaligned, it must be eliminated to form a new reserve pattern. Various layers of material, for example an oxide layer, an aluminum layer, a polysilicon layer, a silicide layer or a polyimide layer, may be present under a resist layer. Therefore, an important consideration for a reserve removal process is the complete removal of a reserve layer, as quickly as possible, and without attack

of an underlying layer.

  A currently widely used reserve elimination agent includes a basic amine such as hydroxylamine, diglycolamine, monoethanolamine or methylethanolamine, and a polar solvent such as

  water or an alcohol, as its essential components.

  Since such a conventional stock removal agent cannot completely remove the polymer, a pre-removal step to remove the polymer is further required. The polymer is a material produced by the reaction of components constituting the reserve, such as carbon (C), hydrogen (H) or oxygen (O), and plasma when plasma etching or etching by Reactive Ion (RIE) is performed, using the reserve pattern as a mask. In particular, when a metal layer is formed under the resist pattern, an organometallic polymer is produced. If such a polymer or organometallic polymer is not removed, but remains in a contact hole or a via hole, for example, the contact resistance increases and may

  result from faults in semi- devices

  conductors. So before using the reserve removal agent, a polymer removal agent, for example a nitric acid solution

  (HNO3), must treat the substrate during the pre-

elimination.

  The conventional reserve disposal agent can attack the underlying layers. A typical example of an underlying layer susceptible to attack is a metal layer. The reason for the above is that the reserve removal agent is mainly composed of a basic solvent or water, which easily corrodes the metallic layer. Thus, a post-elimination step to prevent attack must be carried out before performing a post-elimination rinse step. In the post-elimination stage,

  uses for example isopropyl alcohol (IPA).

  Therefore, as a nitric acid treatment step (pre-elimination step) and an IPA treatment step (post-elimination step) are usually also carried out, the reserve elimination process becomes more complicated and the duration of the treatment is prolonged, which consequently decreases the productivity. Also, as a pre-elimination material, for example nitric acid, and a post-elimination material, for example IPA, are further required, as well as the reserve elimination material, manufacturing costs increase . In addition, as the various baths containing nitric acid and IPA are required, the reserve disposal device

  becomes bulky, undesirably.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a reserve elimination method which substantially overcomes one or more of the problems due to

  limitations and drawbacks of the related technique.

  A second object of the present invention is to provide a reserve elimination device for

use in the process.

  Therefore, to achieve the above objects and other objects and advantages of the invention, a reserve removal method involves the provision of a substrate and the formation of a reserve on the substrate. Then the substrate is brought into contact

  with a standby disposal agent comprising an N-

  alkanol-alkoxy-alkanamide, in order to eliminate the reserve on

the substrate.

  According to another aspect of the process of the invention, the substrate is brought into contact with a composition

  reserve disposal having an N-alkanol-alkoxy-

  alkanamide and an attack inhibitor. A material

  polar can be added to this composition.

  According to an alternative aspect of the process of the invention, the reserve elimination composition

  includes an alkanolamine and an alkyl alkoxyalkanoate.

  Preferably, the composition comprises an inhibitor

and a polar material.

  In another aspect of the invention, a device for removing a reserve from a substrate comprises a source of a reserve removing agent comprising an N-alkanol-alkoxy-alkanamide. A delivery unit is in fluid communication with the source, through which the reserve disposal agent is delivered. A reserve disposal unit in fluid communication with the delivery unit directs the reserve disposal agent in contact with a substrate disposed in the reserve disposal unit, whereby the reserve is removed from the substrate. In other aspects of the device of the invention, the source is a source of an elimination composition

  reserve. The composition can consist of an N-

  alkanol-alkoxy-alkanamide and an attack inhibitor, or alternatively an alkanolamine and an alkyl alkoxyalkanoate. An attack inhibitor, or polar material, or both, can be added to the

composition issued.

  The resist removal method of the present invention can remove a resist and a polymer completely, by a simple method and in a short time, without attacking the layer underlying the resist. The device can therefore be simpler and smaller.

Brief description of the drawings

  Figure 1 is a diagram in which the solid lines indicate a process for removing a reserve using a reserve removing agent or a reserve removing composition according to the present invention, and the dashed lines indicate the conventional steps eliminated by the use of the present invention; Figure 2 is a block diagram of a reserve disposal device using a reserve elimination agent or a reserve elimination composition according to the present invention; FIG. 3 is a diagram of a horizontal type reserve elimination device using the reserve elimination composition according to the present invention; Figure 4 is a diagram of a vertical type standby device using the standby composition according to the present invention; and FIG. 5 is a graph illustrating the change in the contents of components of the reserve composition, measured by gas chromatography for 48

hours at 8 hour intervals.

  Description of the preferred embodiments

  We will describe below an amide compound, a reserve elimination agent and an elimination composition.

  of reserve, as well as processes for their preparation.

  The present invention relates to a method for eliminating a reserve using them and to a reserve elimination device used in the * method for eliminating reserve, and these will be described in

detail.

  A new amide compound used in the present invention is a Nalcanol-alkoxy-alkanamide. In detail, the N-alkanol-alkoxy-alkanamide is represented by the formula (1):

R4-O-R3-CO-N-R1R2OH (1)

  wherein R1 is a hydrogen atom, a C1 to Cs hydrocarbon (i.e. a non-cyclic hydrocarbon having from 1 to 5 carbon atoms), or an aromatic hydrocarbon having from 1 to 3 rings; R2 is a C1 to C5 hydrocarbon or an aromatic hydrocarbon having 1 to 3 rings; and R3 and R4 are each any of the C1 to C5 hydrocarbons, independently of each other. In the preferred embodiment, R1

  is a hydrogen atom, R2 is -CH2CH2-, R3 is -CH2CH2-

and R4 is -CH3.

  The amide compound used in the present invention contains a hydroxy group (-OH) causing a nucleophilic reaction with a reserve, and an alkoxy group (-OR4) causing a hydrophilic reaction with the hydroxy group (-OH). Therefore, a reserve removal agent having the amide compound according to the present invention is very effective in removing a reserve. Consequently, according to an embodiment of the present invention, the N-alkanol-alkoxy-alkanamide compound itself constitutes a

reserve disposal officer.

  In another embodiment, a composition

  reserve disposal includes N-alkanol-alkoxy-

  alkanamide and an attack inhibitor. Also, the resist removal composition optionally further comprises a polar material having a

dipole moment of 3 or more.

  For example, in the reserve elimination composition, the content of N-alkanol-alkoxy-alkanamide may be from 50 to 99.9 weight percent (% by weight) relative to the total weight of the composition, and the content

  the attack inhibitor can be from 0.01 to 30% by weight.

  In the preferred embodiment, the content of N-

  alkanol-alkoxy-alkanamide is 70 to 90% by weight and the content of the attack inhibitor is 7 to 15% by weight. In addition, the content of the polar material having a dipole moment of 3 or more can be from 0.01 to 30%.

  by weight, and is preferably 3 to 20% by weight.

  N-alkanol-alkoxy-alkanamide is a compound

  represented by formula (1) described above.

  The attack inhibitor is represented by the following formula (2): R6- (OH) n (2) in which R6 is a C1 to C5 hydrocarbon, a C1 to C5 hydrocarbon having a group -COOH, a hydrocarbon aromatic having 1 to 3 rings, or an aromatic hydrocarbon having 1 to 3 rings and a -COOH group in at least one ring. The integer n can have a value from 1 to 4, limits included. In the preferred embodiment, R6 is a benzene ring and the attack inhibitor is catechol, where n is 2. Also, gallic acid is a widely known attack inhibitor represented by the formula (2) , which can be used in the context of the present invention. With regard to the polar material having a dipole moment of 3 or more, water, methanol or dimethyl sulfoxide can be used. The polar material having a dipole moment of 3 or more has high solubility to a crosslinked polymer and a resist. In other words, the polymer strongly bonded to the side walls of the resist pattern and to the surface of the exposed underlying layer can be

  effectively removed by such polar material.

  Also, the elimination of the reserve itself is

  facilitated by such a polar material.

  Another embodiment of a resist removal composition used in the present invention comprises an alkanolamine, which is an amine compound, and an alkyl alkoxyalkanoate, which is an ester compound. Also, it is also possible optionally to incorporate an attack inhibitor or a polar material.

  having a dipole moment of 3 or more, or both.

  For example, in this embodiment, the alkanolamine content is from 10 to 70% by weight relative to the reserve elimination composition, and the content of

  the alkyl alkoxyalkanoate is from 10 to 70% by weight.

  In the preferred embodiment, the alkanolamine constitutes from 30 to 40% by weight and the alkoxyalkanoate

  of alkyl constitutes from 30 to 40% by weight.

  In this example, the content of the attack inhibitor is from 0.01 to 30% by weight relative to the reserve elimination composition. In the preferred embodiment, the attack inhibitor constitutes from 7 to 15% by weight. In addition, the content of the polar material is from 0.01 to 30% by weight relative to the reserve elimination composition. In the preferred embodiment, the polar material constitutes from 3 to

20% by weight.

  The N-alkanolamine which can be used in the present invention is represented by the following formula (3):

R1-NH-R2-OH (3)

  wherein R. is a hydrogen atom, a C1 to C5 hydrocarbon, or an aromatic hydrocarbon having from 1 to 3 rings; and R2 is a C1 hydrocarbon to

  C5, or an aromatic hydrocarbon having 1 to 3 rings.

  In the preferred embodiment, R1 is hydrogen

  and R2 is monoethanolamine, i.e. -CH2CH2-.

  The alkyl alkoxyalkanoate which can be used in the present invention is represented by the following formula (4):

R4-O-R3-COO-R5 (4)

  wherein R3, R4 and R5 are each any of the C1 to C5 hydrocarbons, independently of each other. The preferred alkyl alkoxyalkanoate is methyl methoxypropanoate in which R3 is -CH2CH2-,

R4 is -CH3 and R5 is -CH3.

  Now we will describe the reaction mechanism

  of the composition according to the last embodiment.

  First, as shown in the following reaction formula (5), the exfoliation of a reserve occurs by

  the nucleophilic reaction mechanism of an alkanolamine.

  Also, dissolution occurs by the nucleophilic reaction mechanism of a hydroxy group in the alkanolamine and the hydrophilic reaction mechanism

  of an alkoxy group in the alkyl alkoxyalkanoate.

  Also, the attack inhibitor effectively prevents attack of the underlying layer, specifically of a metal layer. In addition, the polar material, for example water, maximizes the polymer removal action. xC-O * 0 "> OC. OH. *. CVCZN- OH / NNri

NH1FOH H / <H X

HO \% HO (5)

  For reasons of convenience of explanation, the mechanism described in reaction formula (5) relates to the case

in which RI is hydrogen.

  To completely form the composition, the composition can be heated to a temperature ranging from room temperature to approximately 120 C. In the preferred embodiment, the composition is heated to a temperature from approximately 80 ° C. to approximately 90 ° C. preceding aims to accelerate the reaction by the components

  in the reaction formula (5) which leads to N-

  alkanol-alkoxy-alkanamide. Alternatively, a reaction catalyst, such as platinum, can be added to the reaction formula (5) to promote a

faster reaction.

  The reserve removal compositions according to the present invention are expressed in the following Table 1. In Table 1, the proportions of

  preferred compositions are given in parentheses.

  Table 1 - Reserve elimination compositions Composition N-alkanolalkoxy- Alcanol- Alcoxyalkanoate Inhibitor Alkanamide elimination material (% amine (% alkyl (% attack) (% polar (% reserve by weight) by weight) weight) by weight) by weight)

1 50 to 99.9 0.01 to 30

2 50 to 99.9 0.01 to 300.01 to 30

(70 to 90) (7 to 15) (3 to 20)

3 10 to 70 10 to 70

4 10 to 70 10 to 70 0.01 to 30

(30 to 40) (30 to 40)

10 to 70 10 to 70 0.01 to 30 0.01 to 30

  (30 to 40) (30 to 40) (7 to 15) (3 to 20)

  The resist removal agent and the resist removal compositions used in the present invention have excellent ability to remove the resist and the polymer, which is a by-product of

  engraving. Also, they do not attack the under layer

  adjacent to the reserve, for example a metallic layer.

  In addition, the materials described above are cheaper than the components of the compositions.

  conventional reserve disposal.

  The N-alkanol-alkoxy-alkanamide, which is the amide compound of the present invention, is prepared according to

  to the following process of the present invention.

  First, the alkanolamine represented by the formula (3) serving as the amine compound is mixed with an alkyl alkoxyalkanoate represented by the formula (4) serving as the ester compound. The mixing ratio of the alkanolamine and the alkyl alkoxyalkanoate is 1/1 by weight. Then the reaction of the amine is carried out

  and ester to prepare an N-alkanol-alkoxy-

  alkanamide represented by formula (1). To provide sufficient energy for this reaction, the temperature of the mixture is kept at a temperature within

  range from room temperature to around 120 C.

  In the preferred embodiment of the process, the mixture is heated to a temperature in the range of from about 80 C to about 90 C. The stock removal composition 1 is prepared

  or 2 presented in Table 1 by mixing the N-

  alkanol-alkoxy-alkanamide prepared as above with an attack inhibitor or material

  polar, or both, as appropriate.

  Also, composition 1 or 2 can be prepared according to the following process. First of all, 10% by weight of alkanolamine and 10 to 70% by weight of alkyl alkoxyalkanoate are mixed with 0 to 30% by weight of an attack inhibitor or 0 to 30% by weight of '' or both. Then, the temperature of the mixture is maintained at a temperature in the range from room temperature to about 120 C. In the preferred embodiment of this process, the mixture is heated to a temperature in the range from about 80 C to about 90 C. The reaction time, i.e. the reaction time, is from about 1 to about 24 hours, preferably from about 1 to about 12 hours. Once heating is complete, the reagent is left alone for 1 to 7 hours to allow the

  chemical reagents to stabilize.

  As a result, a composition is obtained which is substantially composed of N-alkanol-alkoxy-alkanamide and the attack inhibitor or polar material or both. Small amounts of alkanolamine may remain

  and unreacted alkyl alkoxyalkanoate.

  The completion of the reaction can be checked visually or by gas chromatography. In the visual verification, the disappearance of the phase separation of the components is observed as the reaction progresses. When a complete disappearance of the separate component layers is observed, it is assumed that the reaction is complete. When we analyze the composition using gas chromatography,

  the area, expressed as a percentage, of N-alkanol-alkoxy-

  alkanamide, exceeding 80%, implies the completion of the reaction. The area in percentage is defined as the area under the peak of the gas chromatography spectrum associated with a component, divided by the sum of the areas under all the peaks of all the components, and the

quotient is multiplied by 100.

  In the preparation of compositions 3 to 5, the components are mixed in the proportions indicated in Table 1, then they are left to react at a temperature in the range from room temperature to approximately 120 ° C. for 1 to 24 hours. Typically, these compositions 3 to 5 are formed by

  first, before using them to eliminate the reserve.

  However, if it is possible to adjust the temperature in the above temperature range while the compositions 3 to 5 are in contact with the reserve, the step

  separate reaction described above can be omitted.

  The reserve elimination method according to the present invention will be described with reference to the solid line steps in FIG. 1. It will be noted that the conventional method is represented by the steps both in

  solid lines than in broken lines in Figure 1.

  Various processes are carried out to complete a semiconductor device, for example an etching process (dry or wet) or an ion implantation process, using a resist pattern as a mask. Next, a substrate, on which the resist pattern is formed, is allowed to come into contact with a resist removal agent or a composition indicated in Table 1 in order to remove the resist or the polymer or both. (step 110). This is achieved by placing the stock removal agent or stock composition in a bath and then immersing the substrate in the bath. Alternatively, the stock removal agent or the stock removal composition can be sprayed onto the substrate by moving the substrate in the spray. The stock removal agent is formed, and the stock removal compositions 1 and 2 are mixed, which can then be brought immediately into contact with the substrate to remove the stock in the removal step. The compositions 3 to 1 indicated in Table 1 are mixed first, and then they can also be left immediately in contact with the substrate; however, it is preferable to give time to the compositions 3

  to 5 to react before carrying out the elimination step.

  The reaction is carried out at a temperature in the range from room temperature to about 120 C for 1 to 12 hours, and this reaction can take place even without heating. In the preferred embodiment, the compositions do not come into contact with the substrate with the reserve before an additional time has elapsed after the completion of the reaction, that is to say 1 to 7 additional hours after the end of the reaction. completion of the reaction. Using these compositions, the reserve removal process can be carried out at a low temperature, 70 C or less, and specifically in the range of 45 C to 70 C. A contact time in the range is preferred. range from about 10 to about 30 minutes. Alternatively, when the structures formed on the substrate have a high thermal resistance, the unheated compositions 3 to 5 can be placed in a reserve elimination unit in contact with the substrate. Then, the temperature of the reserve removal unit can be adjusted to the temperature at which the amine and the ester can react, within the range of room temperature and beyond, to form the amide. Then, the reaction in which the amide is formed by the composition, and the reaction in which the resist is removed from the substrate, can take place at the same time. Namely, in this case, the separate reaction step can be omitted from the elimination step to

compositions 3 to 5.

  The resist material, i.e., the resist agent or the resist composition, can be applied to a resist suitable for short wavelength exposure, such as a reserve for an ArF excimer laser (193 nm), as well as a reserve for a conventional line i source (365 nm), or else a reserve for a

excimer laser at KrF (248 nm).

  After complete elimination of the reserve, the elimination material for rinsing is removed (step 130).

  reserve and the dissolved reserve remaining on the substrate.

  The rinsing step is carried out using a rinsing solution, for example demineralized water. If necessary, the rinsing step can be carried out in two stages. Finally, the substrate is dried by a centrifugal drying method or a drying method using isopropyl alcohol, for example, as a drying agent, to remove the demineralized water remaining on

the substrate (step 140).

  After the drying step 140, the substrate is transferred for further processing. When a reserve mask is formed in a subsequent step, the reserve is then removed by the steps indicated in Figure 1 after completion of this subsequent step. The semiconductor device is terminated by such methods of

  manufacture of standby units and disposal steps.

  As shown in Figure 1, as the resist removal material used in this invention has an excellent ability to remove the resist or polymer, the pre-elimination step 100 (broken lines) is not necessary, unlike the case of conventional technique. Also, since the layer underlying the reserve is not attacked, the post-elimination step 120 (broken lines) can be omitted, also unlike in the case of the conventional technique. Thus, according to the present invention, the reserve can be completely eliminated by a simpler method, compared to the conventional reserve elimination method. Therefore, the productivity of semiconductor devices can be

significantly increased.

  Also, as described above, since the reserve elimination method is simplified, the reserve elimination device according to the present invention can

  be made smaller or more compact.

  Referring to Figure 2, a reserve disposal device 200 according to the present invention simply comprises a reserve elimination unit 210, a rinsing unit 220 and a drying unit 230. Namely, the pre-unit -conventional and conventional post-elimination unit is not necessary. Thus, the surface occupied by the reserve elimination device 200 can be significantly

  reduced compared to conventional technique.

  The reserve disposal unit of the present invention is in fluid communication with a source of the reserve disposal material used in the

  method of the present invention.

  In the case where the reserve elimination device 200 employs an immersion process, the units 210, 220 and 230 each correspond to an independent bath. Thus, unlike the conventional technique, a pre-elimination nitric acid (HNO3) treatment bath and a post-elimination isopropyl alcohol (IPA) treatment bath are not necessary, which eliminates by consequently two baths and significantly reduces the surface occupied by the

  reserve disposal device 200. Reserve disposal devices employing a process by

  spray can be classified into a

  horizontal type and vertical type.

  Referring to Figure 3, a horizontal type reserve disposal device 300 employs horizontal support means 340, for example a conveyor system, and is divided into a reserve disposal unit 310, a rinsing unit 320 and a drying unit 330. A source 360 of resist material contains either an N-alkanol-alkoxy-alkanamide or an alkanolamine and an alkyl alkoxyalkanoate. The source is in fluid communication with the reserve disposal unit 310, for example, through a delivery unit 370. Conventional sources 362 and 364 for a rinse solution and a drying agent, respectively , are also incorporated, and can also be connected in fluid communication with the respective units 320 and 330, via the delivery unit 370. Nozzles 312, 322 and 332 are installed in the units for the materials of spraying suitable for the functions of the respective units. In particular, the nozzle 312 is installed in the reserve disposal unit 310. In operation, when a substrate is loaded in the reserve disposal unit 310, a reserve disposal material of the present invention is

  sprayed from nozzle 312 to eliminate the reserve.

  Then, the substrate is continuously conveyed horizontally, by the conveyor system 340, to the rinsing unit 320. A rinsing solution is sprayed into the rinsing unit 320 via the nozzle 322. Finally, the substrate is conveyed into the drying unit 330 by the conveyor system 340 so as to be then dried by a drying agent, such as air or a drying chemical directed onto the substrate by the nozzle 332. As the elimination device reserve of the horizontal type comprises only three units, the size of the device is significantly reduced. Referring to Figure 4, a vertical type back-up device 400 employs a vertically movable substrate holder 440. The vertical type also includes a source 460 of the back-up materials of the present invention and a unit of issue 470 to deliver the reserve disposal material. In the embodiment

  preferred, the substrate holder 440 can rotate.

  Also, the interior of the device is constructed of three zones with a platform structure, vertically displaced with respect to each other, and not of independent chambers. Namely, the units are composed of a drying zone 430, a rinsing zone 420 and a reserve elimination zone 410, in vertical sequence. Sources 462 and 464 for the rinse solution and a drying agent, respectively, can also be incorporated, and these materials can be delivered through the delivery unit 470. In the exemplary embodiment, a line single feed 450 delivers

  respective materials to all three units.

  For example, when a substrate is loaded on the substrate support 440, the support 440 first moves to an area where the stock removal is performed and the stock removal material from the source of stock removal. reserve 460 through the delivery unit 470 is sprayed through the delivery line 450. In the preferred embodiment, the reserve removal material is discharged outward through an evacuation pipe (not shown). When the reserve removal step is complete, the substrate holder 440 moves the substrate to the rinsing unit 420 downward. A rinsing solution is then sprayed into the rinsing unit 420 by

  through the delivery line 450.

  Finally, the substrate is then carried to the drying unit 430 by the vertical movement of the support of

substrate 440 to be dried.

  Although Figure 4 shows that the drying unit 430, the rinsing unit 420 and the reserve disposal unit 410 are arranged vertically in sequence from the bottom up, these units can be arranged

  vertically in reverse order.

  Since the vertical type reserve disposal device of the present invention also only includes three units, the size of the device is significantly reduced compared to a device

of the conventional vertical type.

  The other details of the present invention are described with reference to the following examples, but it should be understood that the invention is not limited to these modes

specific achievements.

Example I

  Preparation of N-ethanol-methoxy-propanamide In this example, 200 ml of monoethanolamine, as alkanolamine, are mixed with 200 ml of methyl methoxypropanoate, as ester. Then the mixture is heated to 90 ° C. for 5 hours. After heating, the reagent is restored to the temperature

room for 5 hours.

  The resulting material is analyzed by chromatography

  gas to determine that the product N- was obtained

  ethanol-methoxy-propanamide. In addition, the product is analyzed using a proton nuclear magnetic resonance spectrum (1 H NMR). The NMR data for the product are as follows: 6.8 ppm (1H), 3.7 ppm (4H),

  3.5 ppm (3H) and approximately 2.8 ppm (1H).

Example II

  Preparation of N, N-t-butyl-ethanol-methoxy-propanamide

  In this example, 200 ml of N, N-t-butyl- are mixed.

  ethanolamine, as alkanolamine, and 200 ml of methyl methoxypropanoate, as ester. Then the mixture is heated to 90 ° C. for 5 hours. After heating, the reagent is restored to the temperature

room for 5 hours.

  The resulting material is analyzed by chromatography

  gas to determine that the product N, N- was obtained

  t-butyl-ethanol-methoxy-propanamide.

Example III

  Evaluation of an appropriate temperature in the preparation of N-ethanol-methoxy-propanamide In this example, 200 ml of monoethanolamine, as alkanolamine, are mixed with 200 ml of methyl methoxypropanoate, as ester. Then, to determine the temperature suitable for the reaction of

  this amine and this ester, we synthesize N-ethanol-

  methoxy-propanamide at different temperatures, as shown in Table 2, and the time required to complete the synthesis is measured. The time necessary for the completion of the synthesis is determined by the time elapsing until the percentage of area of the amide (N-ethanol-methoxy-propanamide) exceeds 80% during

  analysis by gas chromatography.

Table 2

  Reaction temperatures and times for N-ethanol-

  methoxy-propanamide Reaction temperature (C) 25 35 45 55 65 80 90 Reaction time (h) 55 24 30 7 6 4 3 From the above result, it is understood that the reaction takes place at room temperature, and that the reaction proceeds more quickly at higher temperatures. However, taking into account other processing conditions, it is preferable that the reaction temperature does not exceed 120 C. Thus, the temperature for the preparation of the amide compound according to the present invention is desirably from room temperature at about 120 C. In the preferred embodiment of the process, the reaction temperature is in the range from about 80 C to

about 90 C.

Example IV

  Preparation of a reserve elimination composition and evaluation thereof in the elimination of the reserve As shown in Table 3, seven (7) reserve elimination compositions are prepared with different contents of monoethanolamine (MEA) , methyl methoxypropanoate (MMP), catechol and water. Then, the compositions are heated at 80 ° C. for 5 hours. Then the resulting material is placed at room temperature for 6

  hours to complete the compositions.

Table 3

  Reserve elimination performance of several compositions Article MEA (ml) MMP (ml) Catechol Water (ml) Observatio (g) ns

1 50 350 60 100 O

2 100 300 60 100 O

  3 150 250 60 100 4 200 200 60 100

250 150 60 100

6 300 100 60 100 O

7 350 50 60 100 O

  (O: good; very good;: excellent) The reserve is prepared as follows, on each of 7 sheets of substrates, the reserve to be eliminated by means of the reserve elimination composition described above. First, we form layers of borophosphosilicate glass (BPSG) with a thickness of 5000 A. Then we form a layer of titanium and a layer of titanium nitride each with a thickness of 200 Å, and we heat . Then, a layer of aluminum is deposited

  6000 A thickness, after which it is allowed to flow.

  A layer of titanium nitride, serving as a covering layer, is formed on the aluminum layer, and then an inter-level dielectric layer with a thickness of 10,000 A is formed. Then a reserve is deposited on the inter-level dielectric layer and a photolithography is carried out to form a reserve pattern defining an interconnection hole. We bake the pattern of

  reserve then the inter-dielectric layer is etched

  levels, using the resist pattern as a mask, using a buffered oxide type etchant to form a via hole exposing the

aluminum layer.

  After forming the interconnection hole, the 7 substrates are immersed in 7 respective baths containing the 7 respective compositions indicated in Table 3. The temperature of the baths is maintained at 60 ° C. After 20 minutes of immersion, the substrates are rinsed with water for 5 minutes and dried, then the substrates are examined using a scanning electron microscope (SEM). The substrates are rated good, very good or excellent based on SEM observations, and the ratings are shown in Table 3 using symbols. The state of the substrate is characterized by the relative amounts of remaining polymer and remaining photoresist. The "good" state is a state similar to that obtained by using a conventional reserve elimination composition known to those skilled in the art. The "very good" state is better than that of the conventional case; and the "excellent" state indicates a significant improvement compared to the conventional case.

Example V

  Evaluation of the appropriate treatment time To verify the appropriate treatment time, the composition corresponding to article number 4 in Table 3 is used, and the reserve is eliminated at various treatment times, as indicated in Table 4. The other processing conditions are the same as those of Example IV. Using the SEM, the state of elimination of the reserve and the state of attack of the aluminum layer and of the silicon layer are observed. The symbols in Table 4 representing the disposal status are the same as in the Table

  3. In Table 4, an X indicates that the layer under

is not attacked.

  From the results presented in Table 4, it is observed that a reaction time suitable for removing the reserve comprises times ranging from 10 to 30 minutes.

Table 4

  Reserve elimination performance as a function of time MEA MMP Catechol Water Time Attack or Article suitability observations (ml) (ml) (g) (ml) (min) non-reserve elimination (AI, Si)

1,200 200 60 100 10 (X

2,200 200 60 100 15 X

3,200 200 60 100 20 X

4,200 200 60 100 25 X

200 200 60 100 30 X

(0: very good;: excellent)

* Example VI

  Evaluation of the appropriate treatment temperature To check the appropriate treatment temperature, the composition corresponding to article number 4 in Table 3 is used, and the reserve is eliminated at various treatment temperatures, as indicated in Table 5. The other treatment conditions are the same as those of Example IV. Using the SEM, the state of elimination of the reserve and the state of attack of the aluminum layer and of the silicon layer are observed. Again, an X indicates that the underlying layer does not exhibit the effects of an attack, and a circle indicates that the underlying layer

presents the effects of an attack.

  From the result presented in Table 5, it is observed that a suitable reaction temperature for the removal of the reserve is located in the lower temperature range, from about 45 C to about 70 C, because the underlying layer is not attacked

notably in this range.

Table 5

  Reserve elimination performance as a function of temperature ArtiMEA MMP Catechol Water Tempera- Observations on Attack or co. Yes)

1,200 200 60 100 45 0 X

2,200 200 60 100 50 0 X

3,200 200 60 100 55 X

4,200 200 60 100 60 X

200 200 60 100 65 X

6,200 200 60 100 70 X

  EXAMPLE VII Comparison of Ability to Eliminate Reserve In this example, we form a via using a reserve motif in the same way as in Example 4, we eliminate the reserve with the composition corresponding to the number of article 4 indicated in Table 3, the treatment time is 20 minutes, and the reaction temperature is 60 C. The resulting material is observed using a SEM, and the results of the observation are presented on the Figure

3.

  In a comparative example, the stock is removed using the conventional stock removal composition, the other conditions being the same as those of the examples described above, then the resulting material is observed using a SEM. The results of the observation are shown in Figure 4. When comparing the SEM photographs shown in Figures 3 and 4, it can be seen that the reserve is completely eliminated when using the reserve elimination composition according to the present invention, while the reservation remains in part when the

  conventional reserve disposal composition.

  Also, while the underlying aluminum layer is not etched in the present invention, the aluminum layer is partially etched when using the conventional resist removal composition.

Example VIII

  Consumption of components of reserve elimination composition The quantity of components of the reserve elimination compositions is analyzed by gas chromatography during the reserve elimination for the composition corresponding to the article number 4 indicated in Table 3, at intervals. 8 hours. The results of the analysis are presented in FIG. 5, in which -N- is the percentage of area of the amide, -A- is the

  percentage area of monoethanolamine, and -D-

  is the area percentage of methyl methoxypropanoate, respectively. From the results presented in FIG. 5, it is observed that the surface area of the amide is constant, at around 80%, even after 48 hours have passed. Also, the area percentage of monoethanolamine is constant, at 3.4. The area percentage of methyl methoxypropanoate is reduced from 0.9 to 0.5 after 24 hours, until it becomes practically 0 after 40 hours. Considering that the main active component of the composition according to the present invention is the amide, a small change in the amide content even after 48 hours implies that the composition according to the present invention is not rapidly consumed in the process and can be used for a long time. This means that the composition according to the present invention can increase productivity and can significantly reduce manufacturing costs, unlike the conventional reserve disposal composition.

  which must be replaced every 24 hours.

  The amide compound according to the present invention has an excellent ability to remove a reserve. Thus, the reserve elimination agent having the amide compound or the reserve elimination composition according to the present invention has an excellent ability to eliminate a reserve and can effectively remove a polymer and an organometallic polymer. Also, the layer underlying the reserve may not be attacked. Therefore, when using the stock removal agent or the stock removal composition according to the present invention, it is not necessary to perform a pre-removal step to remove the polymer and a post step -Elimination to prevent attack of the underlying layer. Thus, the reserve elimination process can be simplified and the duration of the treatment can be reduced. Also, the temperature necessary for the elimination of the reserve can be established at a lower temperature. In addition, the standby disposal device can be

  simplified and can be made more compact.

  It will be obvious to those skilled in the art that various modifications and variations of the present invention can be made without departing from the spirit or scope of the invention. Thus, it is intended that the present invention covers the modifications and variations of this invention to the extent that they

  fall within the scope of the appended claims and

their equivalents.

Claims (44)

  1. Reserve elimination method, characterized in that it comprises: the arrangement of a substrate; the formation of a reserve on the substrate; and bringing the substrate into contact with an agent   reserve elimination comprising an N-alkanol-alkoxy-   alkanamide, to eliminate the reserve on the substrate.   2. The method of claim 1, wherein   during said contacting, the N-alkanol-alkoxy-   alkanamide corresponds to formula (1): R4-O-R3-CO-N-R1R2OH (1)   in which: R1 is hydrogen, a C1 to C5 hydrocarbon or an aromatic hydrocarbon having from 1 to 3 rings, R2 is a C1 to C5 hydrocarbon or an aromatic hydrocarbon having from 1 to 3 rings, and   R3 and R4 are independently a C1 to C5 hydrocarbon.   3. The method of claim 2, wherein during said contacting: R1 is hydrogen, R2 is -CH2CH2-, R3 is -CH2CH2-, and R4 is -CH3.   4. The method of claim 1, further comprising: rinsing the substrate; and drying the substrate.   5. The method of claim 1, wherein said contacting is carried out at a temperature in the range from about 45 C to about C. 6. The method of claim 1, wherein said contacting is carried out for a period ranging from about 10 minutes to about 30 minutes. 7. Reserve elimination method, characterized in that it comprises: the provision of a substrate; the formation of a reserve on the substrate; and bringing the substrate into contact with a composition   reserve elimination comprising an N-alkanol-alkoxy-   alkanamide and an attack inhibitor, to eliminate reserve on the substrate.   8. The method of claim 7, wherein   during said contacting, the N-alkanol-alkoxy-   alkanamide corresponds to formula (1): R4-O-R3-CO-N-R1R20H (1)   in which: Ri is hydrogen, a C1 to C5 hydrocarbon or an aromatic hydrocarbon having from 1 to 3 rings, R2 is a C1 to C5 hydrocarbon or an aromatic hydrocarbon having from 1 to 3 rings, and   R3 and R4 are independently a C1 to C5 hydrocarbon.   9. The method of claim 7, wherein during said contacting, the attack inhibitor is a compound of formula (2): R6- (OH) n (2) in which: R6 is a C1 to C5, a C1 to C5 hydrocarbon having a group -COOH, an aromatic hydrocarbon having from 1 to 3 rings, or an aromatic hydrocarbon having from 1 to 3 rings and a group -COOH, and n is an integer from 1 to 4.   10. The method of claim 7, wherein during said contacting: the N-alkanol-alkoxy-alkanamide is present in an amount ranging from about 50 to about 99.9% by weight relative to the composition, and the attack inhibitor is present in an amount in the range of about 0.01 to about 30% by weight based on the composition for eliminating Reserve.   11. The method of claim 7, further comprising mixing a polar material having a dipole moment of not less than about 3 in the resist removal composition, before said completion put in contact.   12. The method of claim 11, wherein during said mixing, the polar material is present in an amount in the range of from about 0.01 to about 30% by weight based on the composition. reserve disposal.   13. The method of claim 7, further comprising: rinsing the substrate; and drying the substrate.   14. The method of claim 7, wherein said contacting is performed at a temperature in the range of about 45 C to about C. 15. The method of claim 7, wherein said contacting is carried out for a period   ranging from about 10 minutes to about 30 minutes.   16. Reserve elimination method, characterized in that it comprises: the provision of a substrate; the formation of a reserve on the substrate; and contacting the substrate with a resist removal composition comprising an alkanolamine and an alkyl alkoxyalkanoate to remove the resist on the substrate.   17. The method of claim 16, wherein during said contacting, the alkanolamine corresponds to formula (3): R1-NH-R2-OH (3)   wherein: R 1 is hydrogen, a C 1 to C 5 hydrocarbon or an aromatic hydrocarbon having 1 to 3 rings; and R2 is a C1 to C5 hydrocarbon or a hydrocarbon aromatic with 1 to 3 cycles.   18. The method of claim 16, wherein during said contacting, the alkyl alkoxyalkanoate corresponds to formula (4): R4-O-R3-COO-R5 (4)   in which R3, R4 and R5 are independently a C1 to C5 hydrocarbon.   19. The method of claim 16, wherein during said contacting: the alkanolamine represents from about 10 to about 70% by weight of the composition, and the alkyl alkoxyalkanoate represents from about 10 to   about 70% by weight of the composition.   20. The method of claim 17, wherein during said contacting: R1 is hydrogen, and R2 is -CH2CH2-.   21. The method of claim 18, wherein during said contacting: R3 is -CH2CH2-, R4 is -CH3, and R5 is -CH3.   22. The method of claim 16, further comprising mixing an attack inhibitor in the stock removal composition prior to completion. of said contacting.   23. The method of claim 22, wherein during said mixing, the attack inhibitor is a compound of formula (2): R6- (OH) n (2) in which: R6 is a C1 to C5 hydrocarbon, a C1 to C5 hydrocarbon having a group - COOH, an aromatic hydrocarbon having from 1 to 3 rings, or an aromatic hydrocarbon having from 1 to 3 rings and a group --COOH, and n is an integer from 1 to 4.   24. The method of claim 22, wherein during said mixing the attack inhibitor is present in an amount in the range of from about 0.01 to about 30% by weight based on the composition reserve disposal.   25. The method of claim 16, further comprising mixing a polar material having a dipole moment of not less than about 3 in the resist removal composition, prior to the completion of said composition. put in contact.   26. The method of claim 25, wherein during said mixing the polar material is present in an amount in the range of from about 0.01 to about 30% by weight based on the composition reserve disposal.   27. The method of claim 16, wherein said contacting is carried out at a temperature in the range from room temperature to about 120 C.   28. The method of claim 16, wherein said contacting is carried out for a period   ranging from about 10 minutes to about 30 minutes.   29. The method of claim 16, further comprising heating the resist removal composition to a temperature in the range of from about room temperature to about 120 C, before said contacting.   30. The method of claim 29, wherein said contacting is performed at a temperature in the range of from about 45 C to about C. 31. The method of claim 16, further comprising: rinsing the substrate; and drying the substrate.   32. A reserve elimination method, characterized in that it comprises: the arrangement of a substrate; the formation of a reserve on the substrate; and contacting the substrate with a resist removal composition to remove the resist on the substrate, the resist removing composition comprising: from about 10 to about 70% by weight, based on the composition, of an alkanolamine, from about 10 to about 70% by weight, based on the composition, of an alkyl alkoxyalkanoate, from about 0.01 to about 30% by weight, based on the composition, of an attack inhibitor, and from about 0.01 to about 30% by weight, based on the composition, of a polar material having a moment   dipole not less than about 3.   33. The method of claim 32, further comprising heating the resist removal composition to a temperature in the range of from about room temperature to about 120 C before said contacting, and wherein the contacting is carried out at a temperature in the range of about 45 C to about 70 C.   34. The method of claim 32, wherein said contacting is carried out at a temperature   ranging from around room temperature to around 120 C.   35. The method of claim 33, wherein said contacting is carried out for a time.   ranging from about 10 minutes to about 30 minutes.   36. The method of claim 34, wherein said contacting is carried out for a time.   ranging from about 10 minutes to about 30 minutes.   37. Device for eliminating a reserve on a substrate, characterized in that it comprises: a source of a reserve elimination agent comprising an N-alkanol-alkoxy-alkanamide; a delivery unit in fluid communication with the source, through which the reserve disposal agent is delivered; and a reserve elimination unit in fluid communication with the delivery unit, for directing the reserve elimination agent in contact with a substrate disposed in the reserve elimination unit, through   whereby the reserve is removed from the substrate.   38. Device for eliminating a reserve on a substrate, characterized in that it comprises: a source of a reserve elimination composition comprising an N-alkanol-alkoxy-alkanamide and an attack inhibitor; a delivery unit in fluid communication with the source, through which the reserve disposal composition is delivered; and a reserve elimination unit in fluid communication with the delivery unit, for directing the reserve elimination composition in contact with a substrate disposed in the reserve elimination unit,   whereby the reserve is removed from the substrate.   39. Device for eliminating a reserve on a substrate, characterized in that it comprises: a source of a reserve elimination composition comprising an alkanolamine and an alkyl alkoxyalkanoate; a delivery unit in fluid communication with the source, through which the reserve disposal composition is delivered; and a reserve elimination unit in fluid communication with the delivery unit, for directing the reserve elimination composition in contact with a substrate disposed in the reserve elimination unit,   whereby the reserve is removed from the substrate.   40. Device for eliminating a reserve on a substrate, characterized in that it comprises: a source of a reserve elimination composition comprising: from approximately 10 to approximately 70% by weight, relative to the composition, d an alkanolamine, from about 10 to about 70% by weight, based on the composition, of an alkyl alkoxyalkanoate, from about 0.01 to about 30% by weight, based on the composition, of an attack inhibitor, and from about 0.01 to about 30% by weight, based on the composition, of a polar material having a dipole moment of not less than about 3; a delivery unit in fluid communication with the source, through which the reserve disposal composition is delivered; and a reserve elimination unit in fluid communication with the delivery unit, for directing the reserve elimination composition in contact with a substrate disposed in the reserve elimination unit,   whereby the reserve is removed from the substrate.   41. The device of claim 37, 38, 39 or, further comprising: a source of a rinse solution; a rinse unit connected to the reserve removal unit and in fluid communication with the source of rinse solution, for rinsing a substrate disposed in the rinse unit with the rinse solution after removal of the reserve; a source of a drying agent; and a drying unit connected to the rinsing unit and in fluid communication with the source of drying agent, for drying the rinsing solution which remains on a substrate disposed in the drying unit with the drying agent. 42. The device of claim 41, wherein: the reserve disposal unit comprises a disposal bath; the rinsing unit comprises a rinsing bath different from the elimination bath; and the drying unit includes a different drying bath   both the elimination bath and the rinsing bath.   43. Device according to claim 41, further comprising a monobloc support connected to the reserve elimination unit, to the rinsing unit and to the drying unit, for horizontally transporting the substrate of the reserve removal to the drying unit through the rinsing unit, and wherein: the reserve removal unit further comprises a first nozzle in fluid communication with the delivery unit, for spraying the substrate with one of the reserve eliminating agent and the reserve eliminating composition, the rinsing unit further comprises a second nozzle in fluid communication with the source of rinsing solution by l intermediary of the delivery unit, for spraying the rinsing solution on the substrate, and the drying unit further comprises a third nozzle in fluid communication with the source of drying agent via the unit dice delivery,   to spray the drying agent on the substrate.   44. The device according to claim 41, further comprising: a vertical substrate support which supports the substrate between the reserve elimination unit, the rinsing unit and the drying unit by a vertical movement; and a delivery pipe in fluid communication, via the delivery unit, with the source of rinsing solution, the source of drying agent, and with a source of a stock removal material, to successively spray the reserve removal material, the rinse solution, and the drying agent toward the substrate, wherein each of the reserve removal unit, the rinse unit and the unit drying material is moved vertically relative to the others, and wherein the stock removal material is one of the stock removal agent and composition reserve disposal.