PL208299B1

Microelectronic cleaning compositions containing oxidizers and organic solvents

Abstract

Cleaning compositions suitable for cleaning microelectronic structures having silicon dioxide, low-κ or high-κ dielectrics and copper or aluminum metallizations contain an oxidizing agent and a polar organic solvent selected from amides, sulfones, sulfolenes, selenones and saturated alcohols, and optionally other components.

Term

Term ended

Expired 27 May 2023, 3.3 years ago.

5 claims: 1 independent, 4 dependent

1
Kompozycja czyszcząca w jednoetapowym procesie element mikroelektroniczny pokryty miedzią i mający niską lub wysoką wartość stałej dielektrycznej z pozostałości o wysokim usieciowaniu lub wysokiej fotoresystywności, pozostałości odczynników do wytrawiania/popiołu w plazmowym procesie, materiałów protektorowych absorbujących światło, powłok przeciwodblaskowych, i zawierających tytan lub tantal, znamienna tym, że zawiera od 0,1 do 30% wagowych nadtlenku wodoru;od 30 do 80% wagowych sulfolanu jako polarnego rozpuszczalnika organicznego o zdolności wiązania wodoru i minimalnie lub bez wykazywania reakcji z czynnikiem utleniającym;od powyżej 0 do 30% wagowych wodorotlenku tetraalkiloamoniowego jako zasadę alkaliczną ;od 0,1 do 5% wagowych czynnika chelatującego lub kompleksującego metal wybranego z grupy obejmującej kwas trans-1,2-cykloheksanodiaminotetraoctowy i kwas etylenodiaminotetrametylenofosfonowy;i od 15 do 50% wagowych wody. PL 208 299 B1
2
Kompozycja według zastrz. 1, znamienna tym, że zawiera od 40 do 75% wagowych polarnego rozpuszczalnika organicznego.
3
Kompozycja według zastrz. 2, znamienna tym, że zawiera sulfolan, wodorotlenek tetrametyloamoniowy, kwas trans-1,2-cykloheksanodiaminotetraoctowy, nadtlenek wodoru i wodę.
4
Kompozycja według zastrz. 2, znamienna tym, że zawiera sulfolan, wodorotlenek tetrametyloamoniowy, kwas etylenodiaminotetrametylenofosfonowy, nadtlenek wodoru i wodę.
5
Zastosowanie kompozycji określonej w zastrz. 1 do jednoetapowego czyszczenia elementu mikroelektronicznego pokrytego miedzią i mającego niską lub wysoką wartość stałej dielektrycznej z pozostałości o wysokim usieciowaniu lub wysokiej fotoresystywności, pozostałości odczynników do wytrawiania/popiołu w plazmowym procesie, materiałów protektorowych absorbujących światło, powłok przeciwodblaskowych, i zawierających tytan lub tantal, przy czym kontaktuje się element mikroelektroniczny z kompozycją czyszczącą w ciągu czasu wystarczającego do usunięcia pozostałości z elementu mikroelektronicznego.

Independent claims5

449 paragraphs in 8 sections, as filed

Description of the invention

The invention relates to a cleaning composition in a single step process, a copper clad microelectronic component and the use of the composition. Compositions for cleaning microelectronic components are particularly preferred, especially those that are useful and have improved compatibility with components containing silicon dioxide, sensitive low or high dielectric and copper metallized components, as well as Al or Al (Cu) metallized components. The invention also relates to the use of such compositions for removing photoresist, removing residues from plasma generated organic, organometallic and inorganic compounds, removing residues from planarization processes such as chemical-mechanical polishing (CMP) and the use of slurry residues as an additive in the planarization process. .

Many photoresist removers and residues have been proposed for use in microelectronics as cleaners in downstream and countercurrent production lines. In the production process, a thin foil of photoresist is deposited on the board and then the digital circuit design is mapped onto it. After drying, the unpolymerized residue is removed with a photoresist developer. Then, the obtained image is transferred to the substrate material, which is generally a dielectric or metal, by plasma etching with reactive gases or chemical solutions. Etching gases or chemical etching solutions selectively attack the unprotected surface of the photoresist.

Moreover, after completion of the etching step, the protective layer must be removed from the protected surface of the wafer so that the final operations can be performed. This can be achieved by using plasma etching with a suitable etchant gas or water based chemical cleaners. However, it is not easy to find a suitable cleaning composition capable of removing the protective layer of the material without deleterious effect, such as e.g. corroding, dissolving or tarnishing the metal circuitry.

As the level of integration of microelectronic systems increases and the size of these devices is reduced, copper metallization of low or high dielectric dielectrics is increasingly used. These materials require finding suitable cleaning compositions. Many process compositions that have previously been applied to traditional or conventional semiconductor devices containing Al / SiO2 or Al (Cu) SiO2 structures cannot be applied to copper metallized low or high dielectric systems. For example, hydroxylamine based stripper or residue strippers have been used successfully to clean Al metallized devices, but are virtually unsuitable for copper metallized systems. Similarly, stripping solutions used for many low K copper metallized systems are not suitable for Al metallized devices unless significant composition changes are applied.

The removal of residues from plasma etching and / or ashing is also a serious problem, especially for components containing materials with a low dielectric constant K and metallized with copper. Incomplete removal or neutralization of these residues can lead to water absorption and the formation of undesirable substances that can corrode the metal structure. The circuitry material is corroded by undesirable substances, discontinuities appear in the circuit, and the electrical resistance adversely increases.

Until now, oxidizing agents have been used mainly in the form of aqueous solutions for purification. Oxidizing agents, such as the commonly used hydrogen peroxide and peroxy acids, react readily or decompose readily, especially in the environment of organic solvents, which are generally used in stripping compositions. In such cases, the oxidizing agent is consumed and can no longer fulfill its role. In addition, microelectronics purification compositions containing oxidizing agents often exhibit poor stability, especially in the presence of significant amounts of 10 wt% or more of organic solvents, and at higher pH values and higher process temperatures. In addition, the stabilizers and solvents used in many compositions often bind the oxidizing agent, thereby reducing its ability to perform the effective oxidation / reduction reaction used in the purification process.

PL 208 299 B1

There is a need for microelectronic cleaning compositions suitable for countercurrent cleaning operations, effective cleaners, suitable for photoresist removal and removal of residues from plasma generated organic, organometallic and inorganic compounds, removal of residues from planarization processes such as CMP, useful, as additives, and which can be used for advanced, bonding materials, containing copper metallized systems and porous or non-porous dielectrics of low (i.e. K = 3 or less) or high (i.e. K = 20 or more) dielectric constant K, as well as suitable for cleaning conventional devices such as aluminum metallized systems or with aluminum (copper), containing silicon dioxide, dielectrics with low or high dielectric constant K.

It has been found that formulations containing an oxidizing agent and certain polar organic solvents that, and particularly those solvents that help stabilize the oxidizing agent, can provide widely acceptable purification compositions. It has been found that solvents with the ability to form hydrogen bonds give just such preparations containing the oxidizing agent.

The invention relates to a cleaning composition in a one-step process, a copper coated microelectronic component having a low or high dielectric constant value from residues with high cross-linking or high photoresistivity, residues of etchant / ash in a plasma process, light-absorbing sacrificial materials, anti-glare, and titanium-containing coatings. or tantalum, characterized by that it contains from 0.1 to 30% by weight of hydrogen peroxide;

from 30 to 80% by weight of sulfolane as a polar organic solvent with a hydrogen binding capacity and with minimal or no reaction with an oxidizing agent; from greater than 0 to 30% by weight of tetraalkylammonium hydroxide as an alkaline base;

from 0.1 to 5% by weight of a chelating or metal complexing agent selected from the group consisting of trans-1,2-cyclohexanediaminetetraacetic acid and ethylenediaminetetramethylenephosphonic acid; and from 15 to 50% by weight of water.

Preferably the composition comprises from 40 to 75% by weight of a polar organic solvent.

Preferably the composition comprises sulfolane, tetramethylammonium hydroxide, trans-1,2-cyclohexanediaminetetraacetic acid, hydrogen peroxide and water.

Preferably the composition comprises sulfolane, tetramethylammonium hydroxide, ethylenedia minotetramethylene phosphonic acid, hydrogen peroxide and water.

The subject of the invention is the use of a composition according to the invention for a one-step cleaning of a micro-electronic component coated with copper and having a low or high dielectric constant value from residues with high cross-linking or high photoresistivity, residues of etching / ash in a plasma process, light-absorbing sacrificial materials, anti-glare coatings , and containing titanium or tantalum, contacting the microelectronic component with the cleaning composition for a time sufficient to remove residues from the microelectronic component.

The cleaning compositions according to the invention may also optionally contain water and / or compatible acids or alkaline bases, chelating agents, co-solvents, oxidizing agent stabilizing agents, metal corrosion inhibitors, surfactants and fluorine compounds. While an alkaline base is an optional ingredient in the cleaning compositions of the invention, it is preferred that the cleaning compositions have an alkaline pH. The alkaline base may be present in an amount of 0 to 30% by weight, preferably in an amount of 0.1 to 10% by weight. The weight percentages provided in this specification are based on the total weight of the cleansing composition.

The countercurrent purification composition of the present invention will contain one or more of any oxidizing agents and polar organic solvents. Purification compositions can be formulated in a highly aqueous, semi-aqueous, or organic solvent environment. The cleaning compositions can be used alone with other solvents only, or can be combined with bases and acids. The purification compositions of the invention can be used over a wide range of process / operation pH and temperature conditions, and can be used to effectively remove photoresist, plasma etch / ashing residues, sacrificial, light-absorbing materials, and anti-reflective coatings (ARCs). Moreover, it has been found that very difficult to clean samples such as highly cross-linked or hardened photoresists and structures containing titanium (such as titanium, titanium oxide and titanium nitride) or tantalum (such as tantalum, tantalum oxide and tantalum nitride) can be easily cleaned with compositions for purification according to the invention.

PL 208 299 B1

The compositions of the invention may contain any oxidizing agent suitable for use in microelectronic cleaning compositions. Examples of such oxidizing agents include, for example, peroxides, especially hydrogen peroxide, molecular adducts of peroxyhydrate with hydrogen peroxide and oxyacids, zirconyl acetate and azo compounds, e.g. sodium percarbonate, sodium perborates as well as periodates (IO4).-), perborohydrates, peroxymanganates (MnO4-), peroxy sulphates, persulphates and alkyloxyhalides, e.g. t-BuOCl. Other peroxy compounds resulting from the substitution of H 2 O 2 and organic molecules can also be used, but less preferably. Examples include alkyl peroxides, peroxy acids, diacylperoxides, and ketone peroxides. Similar products of the substitution of H2O2 with inorganic molecules, such as peroxosulfuric acid, can also be used. The oxidizing agent is used in the purification compositions of the invention in an amount of 0.1 to 30 wt%, preferably 0.1 to 5 wt%, and most preferably 1 to 5 wt%. The preferred oxidizing agent is hydrogen peroxide (H2O2), preferably used as a 3 to 30% aqueous solution.

The organic solvent is a polar organic solvent with the ability to form hydrogen bonds and having little or no reaction with the oxidizing agent. Such organic solvents include amides, sulfones, sulfolenes, selenones, and saturated alcohols. Among the preferred solvents, mention may be made of: sulfolane (tetrahydrothiophene 1,1-dioxide), 3-methylsulfolane, n-propyl sulfone, n-butyl sulfone, sulfolene (2,5-dihydrothiophene 1,1-dioxide), 3-methylsulfolene, amides such as 1- (2- hydroxyethyl) -2-pyrrolidinone (HEP), dimethylpiperidone (DMPD), N-methylpyrrolidinone (NMP) and dimethylacetamide (DMAc), dimethylformamide (DMF), and saturated alcohols such as ethanol, propanol, butanol, hexanol, ethylene glycol, propylene glycol , glycerol and hexafluoroisopropanol. Organic solvent - A component of the composition may include one or more solvents and is generally present in an amount from 1 to 99.9% by weight, preferably in an amount from 10 to 90% by weight, and most preferably in an amount from 30 to 80% by weight. These solvents are resistant to acidic and alkaline environments and do not bind too strongly to the oxidizing agent. Moreover, they are capable of stabilizing an oxidizing agent such as hydrogen peroxide by forming stable complexes through interaction such as hydrogen bonding.

Water may be present in the cleansing compositions in an amount from 0.1 to 98% by weight, preferably in an amount from 10 to 60% by weight, most preferably in an amount from 15 to 50% by weight. Water may be part of other ingredients and / or may be added additionally.

An alkaline base may optionally be present in the compositions, but is generally a preferred ingredient in the cleansing compositions of the invention. The alkaline base may be present in an amount from 0 to 30% by weight, preferably in an amount from 0.1 to 10% by weight, most preferably in an amount from 0.1 to 5% by weight. Any suitable alkaline base can be used in cleaning compositions. The preferred bases are ammonium hydroxide or a base whether or not derived from ammonia.

If the composition is to be used for the purification of copper metallized structures, the preferred base is one that is not derived from ammonia, and if the composition is to be used for the purification of aluminum containing structures, a more desirable alkali base will be ammonium hydroxide, ammonia or non-ammonia derived bases in combination with an inhibitory base. corrosion with a co-solvent and / or a corrosion inhibiting agent as disclosed below. As examples of suitable non-ammonia bases, mention may be made of tetraalkylammonium hydroxides such as those of formula R4N+OH-wherein each R is independently substituted or unsubstituted alkyl groups, preferably having 1 to 22 carbon atoms and more preferably 1 to 4 carbon atoms. Among the alkaline bases used in the compositions, for example, tetramethylammonium hydroxide, tertrabutylammonium hydroxide, choline hydroxide and the like can be mentioned. As alkaline bases, inorganic bases such as, for example, potassium hydroxide, sodium hydroxide, etc.

As previously noted, the purification composition of the invention may also be used at acidic pH values, and any suitable acidic component, such as, for example, HCl or HF, may be used in an amount sufficient to produce an acidic pH of the composition.

The cleaning composition may also optionally contain one or more corrosion-inhibiting co-solvents. Preferred corrosion-inhibiting cosolvents used in the compositions of the present invention have the following general formula

W- [CR1R2] nY

Wherein R1 and R2 are each independently a substituent selected from H-alkyl, preferably alkyl of 1 to 6 carbon atoms, aryl, preferably aryl of 3 to 14 carbon atoms, OR3 and SO2R4; n is from 2 to 6, preferably 2 or 3; W and Y are each independently a substituent selected from OR3 and SO2R4 and R3 and R4 are each independently a substituent selected from H-alkyl, preferably alkyl having 1 to 6 carbon atoms, and aryl, preferably aryl having 3 to 14 carbon atoms. Examples of such corrosion-inhibiting co-solvents are, for example, ethylene glycol, propylene glycol and glycerol and the like. If the desired polar organic solvent component of the cleansing composition is not a saturated alcohol meeting the formula above, it may be present as a cosolvent. The co-solvents may be present in the composition in an amount from 0 to 80% by weight, preferably from 1 to 50% by weight, most preferably from 1 to 30% by weight.

The compositions of the invention may also contain other corrosion inhibiting agents, preferably aryl compounds containing two or more OH, OR6, and / or SO2R6R7 groups bonded directly to the aromatic ring, wherein R6, R7 and R8 are independently of each other alkyl, preferably alkyl containing from 1 to 6 carbon atoms or an aryl, preferably aryl having 6 to 14 carbon atoms. Examples of such useful corrosion inhibitors are catechol, pyrogallol, gallic acid, resorcinol, etc. The above corrosion inhibiting agents may be present in an amount from 0 to 15% by weight, preferably from 0.1 to 10% by weight, most preferably from 0.5 to 5% by weight.

Organic or inorganic chelating or metal complexing agents are not required but provide significant benefits such as, for example, improved product stability. Examples of suitable chelating or complexing agents include, but are not limited to: trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), ethylenediaminetetraacetic acid (EDTA), stannates, pyrophosphates, alkylidene diphosphonic acid derivatives (e.g. ethane-1-hydroxy-1,1-diphosphonate), phosphonates containing functional residues derived from ethylenediamine, diethylenetriamine or triethylenetetramine e.g. ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid, triethylenetetraaminohexamethylenephosphonic acid. The chelating agent will be present in the composition in an amount from 0 to 5% by weight, preferably from 0.1 to 2% by weight. Various phosphonates, chelating or metal complexing agents such as ethylenediaminetetramethylenephosphonic acid (EDTMP) allow a much greater stabilization of the purification composition according to the invention containing the oxidizing agent in an acidic and alkaline medium and are therefore generally preferred.

Other oxidizing agent stabilizers may also be used in the purification compositions of the invention, if desired. These stabilizers can be used in an amount of from 0 to 10% by weight, preferably from 0.1 to 5% by weight. Examples of such stabilizers include, but are not limited to, acetanilide and silicates, preferably metal ion-free silicates such as tetraalkylammonium silicates (containing hydroxy- and alkoxyalkyl groups), where the alkyl group preferably has from 1 to 4 carbon atoms. Such silicates include tetraethylorthosilicate, tetramethylammonium silicate, tetrakis (2-hydroxyethyl) orthosilicate, etc.

Other metal corrosion inhibitors such as benzotriazole may also be used in an amount of from 0 to 5% by weight, preferably from 0.1 to 2% by weight.

The cleaning compositions may optionally contain surfactants such as e.g. dimethylhexynol (Surfynol-61), ethoxytetramethyl decynediol (Surfynol-465), polytetrafluoroethylene acetoxypropyl betaine (Zonyl FSK), Zonyl FSH etc. The surfactant will generally be present in an amount from 0 to 5 wt%. preferably 0.1 to 3% by weight.

The cleaning compositions may also optionally contain fluorine compounds such as, for example, tetramethylammonium fluoride, tetrabutylammonium fluoride, and ammonium fluoride. Other suitable fluorine compounds include, for example, fluoroborates, tetrabutylammonium fluoroborates, aluminum hexafluorides, antimony fluoride and the like. The fluorine compounds will be present in an amount of from 0 to 10% by weight, preferably from 0.1 to 5% by weight.

Examples of cleaning compositions according to the invention are shown in Tables 1 to 9.

The abbreviations used in the tables mean.

HEP = 1- (2-hydroxyethyl) -2-pyrrolidinone

TMAH = tetramethylammonium hydroxide

TMAF = tetramethylammonium fluoride

ACA = acetanilide

CyDTA = trans-1,2-cyclohexanediaminetetraacetic acid

TEOS = tetraethylorthosilicate

PL 208 299 B1

DMPD = dimethylpiperidone

SFL = sulfolane

TMAS = tetramethylammonium silicate

EG = ethylene glycol

CAT = catechol

EHDP = ethane-1-hydroxy-1,1-diphosphonate

EDTMP = ethylenediaminetetramethylenephosphonic acid

IN HCl = 1 normal hydrochloric acid

NH4OH = ammonium hydroxide

CH = choline hydroxide

Water = additional water, in addition to that contained in the aqueous solution of the ingredients.

Also in the tables below, compositions XM-188, XM-188A and XM-191 refer to the following compositions in which the specified ingredients are present in the parts by weight indicated in parentheses.

XM-188 = SFL (300), water (75), 25% TMAH (25), CyDTA (2.3) XM-188A = SFL (150), water (60), 25% TMAH (17.5), EDTMP (1.8) XM-191 = SFL (150), water (60), 25% TMAH (17.5), EDTMP (1.8), EG (30)

Table 1

Compositions / parts by weight on top of the grid and below weight percentages

<td>Ingredient</td><td>AND</td><td>B</td><td>C.</td><td>D</td><td>E.</td><td>F.</td><td>G.</td>

<td>CyDTA</td><td></td><td> 0,2</td><td></td><td></td><td></td><td> 0,4</td><td> 0,4</td>

<td>EDTMP</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

PL 208 299 B1 cont. table 1

<td>Water</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 30</td><td> 30</td>

<td rowspan="2">SUM ingredients composition</td><td> 49,7</td><td> 50,5</td><td> 50,5</td><td> 49,5</td><td> 49,5</td><td> 100,4</td><td> 100,4</td>

Table 2

Compositions / parts by weight on top of the grid and below weight percentages

<td>Ingredient</td><td>H.</td><td>AND</td><td>J.</td><td>K.</td><td>L.</td><td>M.</td><td>N</td>

<td>CyDTA</td><td></td><td> 0,92</td><td></td><td></td><td> 0,35</td><td></td><td> 0,24</td>

<td>EDTMP</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Water</td><td> 15</td><td> 60</td><td></td><td></td><td></td><td></td><td> 9</td>

PL 208 299 B1 cont. table 2

<td>SUM ingredients composition</td><td> 49 100%</td><td> 200,92 100%</td><td> 57,6 100%</td><td> 42,5 100%</td><td> 68,55 100%</td><td> 35,74 100%</td><td> 55,43 100%</td>

Table 3

Compositions / parts by weight on top of the grate and below

<td>Ingredient</td><td>ABOUT</td><td>P.</td><td>Q</td><td>R</td><td>S.</td><td>T.</td><td>AT</td>

<td>CyDTA</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>EDTMP</td><td></td><td></td><td> 0,68</td><td></td><td></td><td></td><td></td>

<td>Water</td><td> 20</td><td> 70</td><td> 22,5</td><td></td><td> 10,6</td><td> 3,5</td><td></td>

PL 208 299 B1 cont. table 3

<td>TOTAL ingredients</td><td> 245,7</td><td> 311,3</td><td> 69,88</td><td> 62,4</td><td> 65,2</td><td> 53,8</td><td> 62</td>

<td>composition</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td>

Table 4

Compositions / parts by weight on top of the grate and below

<td>Ingredient</td><td>V</td><td>IN</td><td>X</td><td>Y</td><td>WITH</td><td>AA</td><td>BB</td>

<td>CyDTA</td><td> 0,39</td><td></td><td></td><td></td><td> 0,39</td><td></td><td></td>

<td>EDTMP</td><td></td><td></td><td></td><td> 0,6</td><td></td><td> 0,6</td><td> 0,6</td>

<td>Water</td><td> 12,5</td><td></td><td></td><td> 20</td><td> 12,5</td><td> 20</td><td> 30</td>

<td>TOTAL ingredients</td><td> 70,69</td><td> 63,80</td><td> 60,50</td><td> 79,70</td><td> 74,49</td><td> 82,70</td><td> 81,70</td>

<td>composition</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td>

PL 208 299 B1

Table 5

Compositions / parts by weight on top of the grate and below

<td>Ingredient</td><td>CC</td><td>DD</td><td>EE</td><td>FF</td><td>CG</td><td>HH</td><td>II</td>

<td>CyDTA</td><td> 0,39 0,54%</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>EDTMP</td><td></td><td> 0,6 0,74%</td><td></td><td></td><td></td><td></td><td></td>

<td>Water</td><td> 12,5 17,48%</td><td> 20 24,99%</td><td></td><td></td><td></td><td></td><td></td>

<td>SUM ingredients composition</td><td> 71,59 100%</td><td> 80,10 100%</td><td> 64 100%</td><td> 65 100%</td><td> 55 100%</td><td> 67,2 100%</td><td> 42,5 100%</td>

PL 208 299 B1

Table 6

Compositions / parts by weight on top of the grid and below weight percentages

<td>Ingredient</td><td>JJ</td><td>KK</td><td>LL</td><td>MM</td><td>NN</td><td> 00</td>

<td>CyDTA</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>EDTMP</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Water</td><td></td><td> 5</td><td></td><td></td><td></td><td></td>

<td>TOTAL ingredients</td><td> 74,50</td><td> 82</td><td> 92</td><td> 42,5</td><td> 74,5</td><td> 93</td>

<td>composition</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td>

Table 7

Compositions / parts by weight on top of the grid and below weight percentages

<td>Ingredient</td><td>PP</td><td>QQ</td><td>RR</td><td>SS</td><td>TT</td><td>UU</td><td>IN</td>

<td>CyDTA</td><td> 3</td><td> 3</td><td> 2,5</td><td> 1,5</td><td></td><td></td><td> 0,23</td>

PL 208 299 B1 cont. table 7

<td>EDTMP</td><td></td><td></td><td></td><td></td><td> 1,8</td><td> 1,8</td><td></td>

<td>Water</td><td> 35</td><td> 45</td><td> 45</td><td> 45</td><td> 50</td><td> 50</td><td> 7,5</td>

<td>compo-</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td>

<td>position</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

Table 8

Compositions / parts by weight on top of the grate and below

<td>Ingredient</td><td>WW</td><td>XX</td><td>YY</td><td>ZZ</td><td>AAA</td><td>BBB</td><td>CCC</td>

<td>CyDTA</td><td> 0,39 0,52%</td><td></td><td> 0,39 0,55%</td><td></td><td> 0,28 0,21%</td><td> 1,2 2,19%</td><td> 0,8 0,63%</td>

PL 208 299 B1 cont. table 8

<td>EDTMP</td><td></td><td> 0,6</td><td></td><td> 0,6</td><td></td><td></td><td></td>

<td>Water</td><td> 12,5</td><td> 20</td><td> 12,5</td><td> 20</td><td> 40</td><td> 25</td><td> 25</td>

<td>ingredients composition</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td><td> 100%</td>

Table 9

Compositions / parts by weight on top of the grid and below weight percentages

<td>Ingredient</td><td>ODD</td><td>EEE</td>

<td>CyDTA</td><td> 0,6 0,50%</td><td> 1,2 0,98%</td>

PL 208 299 B1 cont. table 9

<td colspan="2">EDTMP</td><td colspan="2"></td><td colspan="4"></td>

<td>Water</td><td></td><td colspan="2"> 25</td><td></td><td></td><td> 25</td><td></td>

<td colspan="2">Composition ingredients</td><td colspan="2"> 100%</td><td></td><td colspan="2"> 100%</td><td></td>

<td>Composition</td><td>SFL</td><td>Water</td><td>25% TMAH</td><td>CyDTA</td><td>EDTMP</td><td>EG</td><td>SUM syntax-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>of the composition</td>

The etch rates of copper and aluminum by the purification compositions of the invention are shown in Table 10. The etch rate was determined using the following procedure.

Pieces of aluminum or copper foil with approximate dimensions of 13 x 50 mm were used for the tests. The thicknesses of the pieces of foil were measured. After cleaning with 2-propanol, distilled water and acetone, the foil pieces were dried in a high-temperature dryer. The cleaned and dried foil pieces were then placed in loosely sealed bottles containing the heated cleaning compositions of the invention and placed in a vacuum oven for two to four hours at the temperature indicated. After the above treatment, the cleaned film pieces were removed from the dryer and bottles, rinsed with copious amounts of distilled water, dried in a high temperature dryer for about 1 hour and allowed to cool to room temperature, then the etching rate was determined by weight loss or change.

PL 208 299 B1

Table 10

<td>Composition according to the tables 1 to 6</td><td>Digestion speed Al at temperature 45 ° C (A / min)</td><td>Etching rate of Al at 65 ° C (A / min)</td><td>Digestion speed Cu at temperature 45 ° C (A / min)</td><td>Digestion speed Cu at temperature 65 ° C (A / min)</td>

<td>Hydroxylamine based coating stripping composition (EKC-265)</td><td>Compatible</td><td>Compatible</td><td>Incompatible</td><td>Incompatible</td>

Dielectric interlayer (ILD) etching rates of compositions JJ and NN (Table 6) of the invention, against different dielectrics, were estimated using the following procedure.

The thickness of the foil on the pieces of tiles is measured using a Rudolph Interferometer. The wafer pieces (with ILD dielectric interlayers deposited on silicon wafers) were immersed in the indicated purification compositions at a specific temperature for a period of 30 minutes, then rinsed with deionized water and dried under a stream of nitrogen. The thicknesses were then re-measured and the etching rates were calculated based on the change in film thickness due to the indicated treatment.

IDL digestion rates were as follows for the compositions: JJ (Table 11), NN (Table 12), HH (Table 13), FF (Table 14), and GG (Table 15).

Table 11

<td>Dielectric</td><td>Etching speed at 70 ° C (A / min)</td>

<td>Carbon doped oxide (CDO)</td><td> <1</td>

<td>Silicon nitride (SiN)</td><td> <1</td>

<td>Tetraethylorthosilicate (pTEOS)</td><td> <1</td>

<td>Organic polymer SILK ™</td><td> <1</td>

<td>Fluorinated Silicate Glass (FSG)</td><td> <1</td>

<td>FOx-16 ™ oxide suspension</td><td> <1</td>

<td>Coral ™ Carbon Oxide</td><td> 3</td>

<td>Black Diamond ™ Carbon Oxide</td><td> 9,5</td>

PL 208 299 B1

Table 12

<td>Dielectric</td><td>Etching speed at 70 ° C (A / min)</td>

<td>Carbon doped oxide (CDO)</td><td> <1</td>

<td>Silicon nitride (SiN)</td><td> <1</td>

<td>Tetraethylorthosilicate (pTEOS)</td><td> <1</td>

<td>Organic polymer SILK ™</td><td> <1</td>

Table 13

<td>Dielectric</td><td>Etching speed at 60 ° C (A / min)</td>

<td>Carbon doped oxide (CDO) n = 1.40</td><td> <1</td>

<td>Silicon nitride (SiN) n = 2.0</td><td> 3</td>

<td>Tetraethylorthosilicate (pTEOS) n = 1.46</td><td> 1</td>

<td>Organic polymer SiLK ™ n = 1.63</td><td> <1</td>

Table 14

<td>Dielectric</td><td>Etching speed at 60 ° C (A / min)</td>

<td>Carbon doped oxide (CPO) n = 1.40</td><td> <1</td>

<td>Silicon nitride (SiN) n = 2.0</td><td> 2</td>

<td>Tetraethylorthosilicate (pTEOS) n = 1.46</td><td> 1</td>

<td>Organic polymer SiLK ™ n = 1.63</td><td> <1</td>

Table 15

<td>Dielectric</td><td>Etching speed at 60 ° C (A / min)</td>

<td>Carbon doped oxide (CPO) n = 1.40</td><td> <1</td>

<td>Silicon nitride (SiN) n = 2.0</td><td> 2</td>

<td>Tetraethylorthosilicate (pTEOS) n = 1.46</td><td> 1</td>

<td>Organic polymer SILKT.M n = 1.63</td><td> <1</td>

The purification ability of the compositions according to the invention is illustrated by the following tests, in which the microelectronic system consisting of a plate with the structure: photoresist / carbon-doped oxide / silicon nitride / copper with a perforated layer of silicon nitride revealing copper, was immersed in cleaning solutions at a specific temperature and for the indicated period of time, then rinsed with water, dried and the degree of purification was determined by SEM measurements. The results are shown in Table 16.

PL 208 299 B1

Table 16

<td>Composition</td><td>G.</td><td>H.</td><td>OO</td>

<td>Purification conditions and results</td><td>35 ° C / 30 minutes 100% purity</td><td>55 ° C / 20 minutes 100% pure</td><td>70 ° C / 20 minutes 100% cleanliness</td>

The purification ability of the compositions according to the invention is also illustrated by the following tests, in which the microelectronic system consisting of an aluminum plate with the structure: namely TiN / Al / TiN / Ti / Si, was immersed in cleaning solutions at a specific temperature and for a specified period of time, then rinsed with water, dried and the degree of purification was determined by SEM measurements. The results are shown in Table 17.

Table 17

<td>Composition</td><td>IN</td>

<td>Purification conditions and results</td><td>55 ° C / 20 minutes 100% purity with perfect compatibility substrate-</td>

The etching rates of aluminum by the purification compositions of the invention are shown in Table 18. The etch rate was determined using the following procedure.

Pieces of aluminum foil with approximate dimensions of 13 x 50 mm were used for the measurements. The thicknesses of the foil pieces were measured. After cleaning with 2-propanol, distilled water and acetone, the foil pieces were dried in a high-temperature dryer. The cleaned and dried foil pieces were then placed in loosely closed bottles containing heated cleaning compositions of the invention and placed in a vacuum oven for two to four hours at the indicated temperature.

After the above treatment, the cleaned film pieces were removed from the dryer and bottles, rinsed with copious amounts of distilled water, dried in a high temperature dryer for about 1 hour and allowed to cool to room temperature, then the etching rate was determined by weight loss or change.

Table 18

<td>Composition according to tables 7 18</td><td>Etching rate of Al at 45 ° C (A / min)</td>

Patent claims

Contents8

58 members in 17 offices

This recordMember, by publication datePriority claim7 more offices are in the list below

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Priority claims
Document	Office	Kind	Date
38680002	United States of America	P	2002-06-07

Members58

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Document	Office	Kind
CA2488735A1	Canada	A1	2003-12-18
CA2488737A1	Canada	A1	2003-12-18
WO03104900A2	World Intellectual Property Organization (WIPO)	A2	2003-12-18
WO03104901A2	World Intellectual Property Organization (WIPO)	A2	2003-12-18
AU2003238773A1	Australia	A1	2003-12-22
AU2003240827A1	Australia	A1	2003-12-22
AU2003240827A8	Australia	A8	2003-12-22
TW200401958A	Taiwan Province of China	A	2004-02-01
WO03104900A3	World Intellectual Property Organization (WIPO)	A3	2004-02-19
WO03104901A3	World Intellectual Property Organization (WIPO)	A3	2004-03-18
TW200407419A	Taiwan Province of China	A	2004-05-16
NO20050075L	Norway	L	2005-01-06
NO20050076L	Norway	L	2005-01-06
KR20050012770A	Republic of Korea	A	2005-02-02
KR20050019103A	Republic of Korea	A	2005-02-28
EP1512050A2	European Patent Office (EPO)	A2	2005-03-09
BR0311827A	Brazil	A	2005-03-29
BR0311827A	Brazil	A	2005-03-29
BR0311830A	Brazil	A	2005-03-29
BR0311830A	Brazil	A	2005-03-29
EP1520211A2	European Patent Office (EPO)	A2	2005-04-06
US2005176602A1	United States of America	A1	2005-08-11
CN1659480A	China	A	2005-08-24
CN1659481A	China	A	2005-08-24
PL373809A1	Poland	A1	2005-09-19
PL374021A1	Poland	A1	2005-09-19
JP2005529363A	Japan	A	2005-09-29
JP2005529487A	Japan	A	2005-09-29
US2005239673A1	United States of America	A1	2005-10-27
IL165580A0	Israel	A0	2006-01-15
IL165581A0	Israel	A0	2006-01-15
IN2744CH2004A	India	A	2006-02-10
IN2761CH2004A	India	A	2006-02-10
IN2762CH2004A	India	A	2006-02-10
ZA200409622B	South Africa	B	2006-05-31
ZA200409621B	South Africa	B	2006-07-26
RS106204A	Serbia	A	2007-02-05
RS106104A	Serbia	A	2007-04-10
US7419945B2	United States of America	B2	2008-09-02
EP2034365A2	European Patent Office (EPO)	A2	2009-03-11
IL165580A	Israel	A	2009-05-04
IL165581A	Israel	A	2009-06-15
JP4304154B2	Japan	B2	2009-07-29
MY139208A	Malaysia	A	2009-08-28
JP4330529B2	Japan	B2	2009-09-16
EP2034365A3	European Patent Office (EPO)	A3	2009-11-11
TWI322827B	Taiwan Province of China	B	2010-04-01
KR100958068B1	Republic of Korea	B1	2010-05-14
KR100958069B1	Republic of Korea	B1	2010-05-17
RS50930B	Serbia	B	2010-08-31
TWI330766B	Taiwan Province of China	B	2010-09-21
PL207297B1	Poland	B1	2010-11-30
MY142745A	Malaysia	A	2010-12-31
PL208299B1This record	Poland	B1	2011-04-29
CN102061228A	China	A	2011-05-18
CN102135735A	China	A	2011-07-27
CN102061228B	China	B	2013-02-13
US8906838B2	United States of America	B2	2014-12-09

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2013-07-31	Decisions on the lapse of the protection rightsLapsedLAPS	LAPS
2012-05-31	Rectifications of patent specificationRECP	RECP

Microelectronic cleaning compositions containing oxidizers and organic solvents

Abstract

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PL 208 299 B1

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PL 208 299 B1

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