CN1184672C - Method of treating fluorosilicic glass surface layer - Google Patents
Method of treating fluorosilicic glass surface layer Download PDFInfo
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- CN1184672C CN1184672C CNB011409150A CN01140915A CN1184672C CN 1184672 C CN1184672 C CN 1184672C CN B011409150 A CNB011409150 A CN B011409150A CN 01140915 A CN01140915 A CN 01140915A CN 1184672 C CN1184672 C CN 1184672C
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Abstract
The present invention provides a method for the surface treatment of a fluorine silica glass (FSG) layer, which comprises the following steps: a fluorine silica glass layer is deposited on a semiconductor chip, and then partial fluorine ions on the upper surface of the fluorine silica glass layer are removed in situ; a silica layer is coated with a photoresist layer, and a predetermined latent pattern is formed in the photoresist layer by an exposure manufacturing technology; the photoresist layer of the predetermined latent pattern is removed by a development manufacturing technology, and the silica layer corresponding to the lower part of the predetermined latent pattern is exposed. The method of the present invention can solve the problems that the photoresist is damaged, the metal is corroded, and the reliability is low because the fluorine ions in the fluorine silica glass are diffused to the surface of fluorine silica glass and form hydrofluoric acid.
Description
Technical field
The present invention relates to a kind of surface treatment method, particularly relate to a kind of fluorine silex glass (fluorinatedsilicate glass, FSG) method of laminar surface processing.
Background technology
Along with the live width of semiconductor fabrication process is more and more thinner, the dielectric layer of each metal interconnecting interlayer must have characteristics such as low-k, the good ditch ability of filling out (gap-filling properties), stable mechanical strength (mechanical stability) and low water absorbable.The dielectric constant that reduces dielectric layer can be avoided the speed of effect of parasitic capacitance signal transmission.Silicon dioxide was most typical dielectric material in the past, but its dielectric constant (k～4) is higher for present manufacture craft, the substitute is and have the more material of low-k, for example fluorine silex glass (fluorinated silicate glass, FSG) (k～3.5).Because fluorine is the electrical atom of a kind of reinforcing yin essence (electronegative atom), so can reduce the polarity (polarizability) of the Si-O-F network structure (SiOF network) in this silica (silicon oxide) dielectric layer effectively, thereby reduce the dielectric constant of this silicon oxide dielectric layer.In addition, because fluorine also is a kind of strong etching media (etching species), so when deposition FSG dielectric layer, the previous FSG film that deposits of fluorine meeting etching, produce precipitation/etching effect (deposition/etching effect), thereby can in the more and more thinner semiconductor fabrication process of live width, form the FSG thin layer of a no hole (void-free).
Please refer to Fig. 1 to Fig. 3, Fig. 1 to Fig. 3 forms the method schematic diagram that limits (patterned) photoresist for having now in fluorine silex glass (FSG) laminar surface, at first, as shown in Figure 1, semiconductor chip 10 comprises a substrate 12, one fsg film 14 is deposited in the substrate 12, and a photoresist layer 16 is covered on the fsg film 14.As shown in Figure 2, carry out exposure (exposing) manufacture craft, in photoresist layer 16, to form a predetermined potential pattern 16a.As shown in Figure 3, carry out a development manufacture craft, utilize the existing known method of this operator, to remove the predetermined potential pattern 16a in the photoresist layer 16, to expose the fsg film 14 of predetermined potential pattern 16a below.
Obtain fluorine silex glass owing in silicon dioxide, adding fluorine ion, yet be present in fluorine ion in the fsg film 14 and unstable, diffuse to the surface of fsg film 14 easily because of the heat treatment in the follow-up manufacture craft than low-k.And the fluorine silex glass have strongly hydrophilic (hydrophilic) hydrone can be attracted to the surface, thereby make fluorine ion and hydrone form hydrofluoric acid (HF), and hydrofluoric acid can react to each other with photoresist layer 16 and makes photoresist be subjected to poisoning (poison), make the photoresist of staying after the development on the chip have the sidewall of non-perpendicular (non-vertical), even can cause the photoresist situation (as shown in Figure 3) of collapsing, thereby can not accurately figure be transferred on the chip from photoresist.In addition, hydrofluoric acid not only increases the resistance of metal, but also may cause reliability (reliability) problem of integrated circuit if touching metal also can cause corrosion of metal.
Summary of the invention
(fluorinated silicate glass, the FSG) method of laminar surface processing is to address the above problem to the object of the present invention is to provide a kind of fluorine silex glass.
The object of the present invention is achieved like this, promptly provide a kind of fluorine silex glass (this method includes following several key step for fluorinated silicateglass, the FSG) method handled of laminar surface:
(1) deposition one fsg film on the semiconductor chip;
(2) upper surface of on-the-spot this fsg film of (in-situ) oxidation is to form the silica layer of a thickness greater than 100 dusts; On this silica layer, apply a photoresist layer;
(3) exposure (exposing) this photoresist layer is to form predetermined potential (latent) pattern in this photoresist layer; And
(4) development (developing) this photoresist layer to remove this photoresist layer of this predetermined potential pattern, exposes this silica layer with respect to this predetermined potential pattern below.
The method that the present invention also provides a kind of fluorine silex glass (FSG) laminar surface to handle, this method includes the following step:
In a chemical vapor deposition (CVD) reaction cabin, deposit a fsg film in the semiconductor chip surface;
In this CVD reaction cabin, a upper surface of on-the-spot this fsg film of (in-situ) oxidation is to form the silica layer of a thickness greater than 100 dusts;
On this silica layer, apply a photoresist layer;
Exposure (exposing) this photoresist layer is to form predetermined potential (latent) pattern in this photoresist layer; And
Development (developing) this photoresist layer to remove this photoresist layer of this predetermined potential pattern, exposes this silica layer with respect to this predetermined potential pattern below.
The present invention utilizes one to contain oxygen plasma, and the part fluorine ion in the upper surface shallow-layer of " on-the-spot (in-situ) removes " fsg film forms the thin silica layer that a thickness is about 100 to 200 dusts with the upper epidermis at fsg film.
The advantage of the inventive method is: (1) fsg film is after utilization contains oxygen plasma " scene removes " fluorine ion, and its physical property (comprising film thickness, refractive index and dielectric constant values etc.) is constant; (2) utilize this thin silica layer to prevent that the fluorine ion of fsg film is to outdiffusion; (3) utilize the interior part fluorine ion of this upper surface shallow-layer that contains oxygen plasma " scene removes " fsg film, reduce the water absorption on fsg film surface; (4) (silicon oxynitride, SiON) on fsg film, the present invention has the manufacturing process steps of minimizing and cost-effective advantage compared with prior art to deposit a silica layer or silicon oxynitride.
Description of drawings
Fig. 1 to Fig. 3 forms the method schematic diagram that limits (patterned) photoresist for having now in fluorine silex glass (FSG) laminar surface;
Fig. 4 and Fig. 5 are for forming the method schematic diagram that limits (patterned) photoresist in fluorine silex glass (FSG) laminar surface among the present invention;
Fig. 6 is a fluorine silex glass film surface material composition analysis result schematic diagram, and wherein PEFSG represents the fluorine silex glass film without any processing, PEFSG (N
2O plasma) then expression process contains the fluorine silex glass film after oxygen plasma removes the top layer fluorine ion.
Concrete implementation content
Please refer to Fig. 4 and Fig. 5, Fig. 4 and Fig. 5 are for forming the method schematic diagram that limits (patterned) photoresist in fluorine silex glass (FSG) laminar surface among the present invention.As shown in Figure 4, semiconductor chip 20 comprises that a substrate 22, one fsg films 24 are deposited in the substrate 22.In preferred embodiment of the present invention, fsg film 24 utilizes a plasma enhanced chemical vapor deposition method (plasma-enhancedchemical vapor deposition, PECVD) or a high density plasma CVD method (high-density plasma chemical vapor deposition, HDPCVD) form, implement environment (not shown) in general chemical vapour deposition reaction cabin and form.Forming the method for fsg film 24, no matter utilize PECVD or HDPCVD, all is that existing this technical staff is known, therefore repeats no more.
After finishing fsg film 24, the inventive method utilizes one to contain oxygen plasma immediately, for example nitrous oxide plasma, oxygen gas plasma, carbon monoxide (CO) plasma, carbon dioxide (CO
2) plasma or other similarly contain oxygen plasma, part fluorine ion in the upper surface shallow-layer (it is thick to be about 100 to 200 dusts) of " on-the-spot (in-situ) removes " fsg film 24 forms a thin silica layer 26 with the upper surface layer in fsg film 24.In preferred embodiment of the present invention, the thickness of silica layer 26 is about 120 dusts (angstrom).Be noted that the thickness of silica layer 26 needs at least greater than 100 dusts, otherwise just can lose the effect that it stops that HF extends out.So-called herein " scene removes " is meant that fsg film 24 and silica layer 26 form in same vapor deposition reaction cabin, and and then silica layer 26 forms after fsg film 24 depositions, utilizes nitrous oxide (nitrous oxide, N
2O) plasma removes the part fluorine ion of the upper epidermis of fsg film 24.The nitrous oxide plasma operations condition that is used for removing part fluorine ion in the fsg film 24 comprises: plasma pressure 0.1 to 10 holder ear (Torr) is preferably 2.4 holder ears (Torr); 0.5 to 10 watt of/square centimeter (W/cm of plasma power
2), be preferably 4.8 watts of/square centimeter (W/cm
2); And 250 to 450 ℃ of plasma temperatures, being preferably 400 ℃, plasma treatment time is 10 seconds.
As shown in Figure 5, one photoresist layer 28 is covered on the silica layer 26, then carry out exposure (exposing) and a development manufacture craft, in photoresist layer 28, to form a predetermined potential pattern and to expose the silica layer 26 of being scheduled to potential pattern below, carry out an etching process at last, the silica layer and the fsg film that are not covered by photoresist are removed (not shown), finish that the predetermined pattern on the photomask is transferred on the semiconductor chip.In the methods of the invention, photoresist layer 28 can be made of a positive light anti-etching agent (positive photoresist) or minus (negative) photoresist.When photoresist layer 28 is when being made of a positive light anti-etching agent, in the exposure process that carries out photochemical conversion (photochemical transformation), light beam can pass an optical mask pattern and expose to photoresist layer 28, and forms a potential pattern (latent pattern) in photoresist layer 28.And then through follow-up development (development) with clean (cleaning) manufacture craft, staying, thereby form a hard mask (hard mask) identical with optical mask pattern not by the photoresist layer 28 that this light beam shone.On the contrary, if photoresist layer 28 is to be made of a negative type photoresist, then just can and be cleaned in the manufacture craft and be eliminated the hard mask that makes 28 formation one of residual photoresist layer and optical mask pattern complementation (complementary) in follow-up development by the photoresist layer 28 that this light beam shone.
Please refer to table, table one contains character that oxygen plasma removes the fluorine silex glass film behind the fluorine ion of top layer relatively for fluorine silex glass film with utilizing, as shown in Table 1, fluorine silex glass film is after containing oxygen plasma treatment, its thickness, refractive index (refractive index, RI) and dielectric constant values (dielectric constant) all with similar without the fluorine silex glass film that contains oxygen plasma treatment, show the part fluorine ion that removes in fluorine silex glass film upper epidermis thickness 100 to 200 dusts thus, little to the physical property influence of fluorine silex glass film.
Table one
Thickness NU (%) refractive index Si-F/Si-O dielectric
(A) at 1 sigma constant value (%) d
PEFSG
a 5060 0.82 1.4321 2.37 3.56
PEFSG(N
2O?plasma)
b 5046 0.82 1.4323 2.37 3.57
aPEFSG is meant undressed fluorine silex glass film.
bPEFSG (N
2O plasma) is meant through containing the fluorine silex glass film of oxygen plasma treatment.
cNU% is meant non-uniformity percentage (non-uniformity% at 1 sigma).
dSi-F/Si-O (%) is meant the ratio of Si-F and Si-O, is to utilize FTIR to measure the back to calculate and get.
Please refer to Fig. 6, Fig. 6 is a fluorine silex glass film surface material composition analysis result schematic diagram, and wherein PEFSG represents the fluorine silex glass film without any processing, PEFSG (N
2O plasma) then expression process contains the fluorine silex glass film after oxygen plasma removes the top layer fluorine ion.As shown in Figure 6, the mass number major part of the material of fluorine silex glass film surface is distributed in 16,17 and 18, by fluorine silex glass film form and the gas componant of surrounding environment is known by inference, the material of aforementioned mass number representative should be O (16), OH (17) and H
2O (18), and the surface of the fluorine silex glass film after containing oxygen plasma treatment has less hydrone, this result shows that this contains the ability that oxygen plasma treatment can reduce the suction of fluorine silex glass film surface, thereby reduces the probability of fluorine ion and hydrone formation hydrofluoric acid.As table one and experimental result shown in Figure 6, show that the part fluorine ion remove fluorine silex glass film top layer is little to the physical property influence of film, diffuse to the probability that fsg film surface and hydrone form hydrofluoric acid but can reduce fluorine ion.
Compare with existing method, the present invention is before depositing photoresist layer 28, utilize a part fluorine ion that contains the upper epidermis of oxygen plasma " scene removes " fsg film 24 earlier, to form a silica layer 26, thereby solve because the fluorine ion in the fsg film 24 can diffuse to the surface of fsg film 24 in follow-up manufacture craft, form hydrofluoric acid (HF) and poison photoresist layer 28 with hydrone, or cause reliability (reliability) problem.In addition, because silica layer 26 is after fsg film 24 forms, utilize one to contain the fluorine ion of oxygen plasma " scene removes " fsg film 24 upper epidermis and form immediately, the time of plasma treatment lacks and is that on-the-spot (in-situ) finishes, and not only can improve manufacture craft efficient and more reduce manufacturing cost simultaneously.
Abovely disclosed the present invention in conjunction with preferred embodiment, all equalizations of doing according to claim of the present invention change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (13)
1. fsg film surface-treated method, this method includes the following step:
Deposition one fsg film on the semiconductor chip;
One upper surface of on-the-spot this fsg film of oxidation is to form the silica layer of a thickness greater than 100 dusts;
On this silica layer, apply a photoresist layer;
This photoresist layer that exposes is to form a predetermined potential pattern in this photoresist layer; And
This photoresist layer that develops to remove this photoresist layer of this predetermined potential pattern, exposes this silica layer with respect to this predetermined potential pattern below.
2. the method for claim 1, wherein the method for this fsg film of oxidation is to utilize one to contain oxygen plasma.
3. method as claimed in claim 2, wherein this to contain oxygen plasma be to utilize nitrous oxide, oxygen, carbon monoxide or carbon dioxide as the oxygen gas of originating.
4. method as claimed in claim 2, wherein this operating condition that contains oxygen plasma includes:
(1). plasma pressure: between 0.1 to 10 holder ear;
(2). plasma power: between 0.5 to 10 watt/square centimeter; And
(3). plasma temperature: between 250 to 450 ℃.
5. the method for claim 1, wherein this fsg film and this silica layer are to form in same chemical vapour deposition reaction cabin.
6. fsg film surface-treated method, this method includes the following step:
In a chemical vapour deposition reaction cabin, deposit a fsg film in the semiconductor chip surface;
In this chemical vapour deposition reaction cabin, a upper surface of on-the-spot this fsg film of oxidation is to form the silica layer of a thickness greater than 100 dusts;
On this silica layer, apply a photoresist layer;
This photoresist layer that exposes is to form a predetermined potential pattern in this photoresist layer; And
This photoresist layer that develops to remove this photoresist layer of this predetermined potential pattern, exposes this silica layer with respect to this predetermined potential pattern below.
7. method as claimed in claim 6, wherein this chemical vapour deposition reaction cabin is to be a plasma enhanced chemical vapor deposition reaction cabin.
8. method as claimed in claim 6, wherein this chemical vapour deposition reaction cabin is to be a high-density plasma enhanced chemical vapor deposition reaction cabin.
9. method as claimed in claim 6, wherein the method for this fsg film of oxidation is to utilize one to contain oxygen plasma.
10. method as claimed in claim 9, wherein this to contain oxygen plasma be to utilize nitrous oxide, oxygen, carbon monoxide or carbon dioxide as the oxygen gas of originating.
11. method as claimed in claim 9, wherein this operating condition that contains oxygen plasma includes:
(1). plasma pressure: between 0.1 to 10 holder ear;
(2). plasma power: between 0.5 to 10 watt/square centimeter; And
(3). plasma temperature: between 250 to 450 ℃.
12. method as claimed in claim 6, wherein this fsg film and dielectric constant that this silica layer recorded jointly are less than 3.6.
13. method as claimed in claim 6, wherein the thickness of this silica layer is between 100 to 200 dusts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011409150A CN1184672C (en) | 2001-09-26 | 2001-09-26 | Method of treating fluorosilicic glass surface layer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011409150A CN1184672C (en) | 2001-09-26 | 2001-09-26 | Method of treating fluorosilicic glass surface layer |
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| Publication Number | Publication Date |
|---|---|
| CN1411041A CN1411041A (en) | 2003-04-16 |
| CN1184672C true CN1184672C (en) | 2005-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011409150A Expired - Lifetime CN1184672C (en) | 2001-09-26 | 2001-09-26 | Method of treating fluorosilicic glass surface layer |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060017166A1 (en) * | 2004-07-20 | 2006-01-26 | Po-Hsiung Leu | Robust fluorine containing Silica Glass (FSG) Film with less free fluorine |
| US7226875B2 (en) * | 2004-11-30 | 2007-06-05 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method for enhancing FSG film stability |
| CN102815663B (en) * | 2011-06-08 | 2015-09-09 | 中芯国际集成电路制造(上海)有限公司 | The preparation method of semiconductor devices |
| CN103871966B (en) * | 2014-03-19 | 2017-05-10 | 武汉新芯集成电路制造有限公司 | Method for restraining fluorosilicone glass crystal defects |
| CN110556295B (en) * | 2019-09-26 | 2021-08-20 | 上海华虹宏力半导体制造有限公司 | Semiconductor device and forming method |
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2001
- 2001-09-26 CN CNB011409150A patent/CN1184672C/en not_active Expired - Lifetime
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