CN109111925A - A kind of wet etching method of etchant and its tantalum nitride membrane - Google Patents

A kind of wet etching method of etchant and its tantalum nitride membrane Download PDF

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CN109111925A
CN109111925A CN201811099131.4A CN201811099131A CN109111925A CN 109111925 A CN109111925 A CN 109111925A CN 201811099131 A CN201811099131 A CN 201811099131A CN 109111925 A CN109111925 A CN 109111925A
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tantalum nitride
nitride membrane
etching
etchant
wet etching
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王进
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Mianyang Zhizhi High-Tech Co Ltd
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Mianyang Zhizhi High-Tech Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00Etching, surface-brightening or pickling compositions
    • C09K13/04Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31105Etching inorganic layers
    • H01L21/31111Etching inorganic layers by chemical means

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention discloses a kind of etchant and its wet etching method of tantalum nitride membrane, the etching solution combination is mainly the mixture of hydrofluoric acid, dodecyl alanine, Phen and water composition.Compared with prior art, the present invention proposes a kind of etch combination for tantalum nitride membrane, when etching for tantalum nitride membrane, can be improved and controls etching speed, and the deterioration of photoresist layer is effectively inhibited, as a result, the etching face of surface flat-satin can be obtained.Existing dry etching technology barrier is broken through, the wet etching technique of tantalum nitride membrane in film resistor field is had developed.The marketization application for promoting tantalum nitride membrane resistance, does one's bit for the fast development of National Electrical information technology.

Description

A kind of wet etching method of etchant and its tantalum nitride membrane
Technical field
The present invention relates to the wet of a kind of film resistor field more particularly to a kind of etchant and its tantalum nitride membrane Method lithographic method.
Background technique
In recent years, with the fast development of electronic information technology, film resistor is due to high resistivity, low resistance temperature Coefficient, high stability, without the good characteristics such as ghost effect and low noise, in aviation, national defence and electronic computer, communication instrument The high frontier such as device, electron exchanger, which has, to be more and more widely used.
Tantalum nitride membrane resistance has the characteristics that fusing point high (3090 DEG C), temperature-coefficient of electrical resistance is small and stability is high.Resistance 180~220 μ Ω/cm of rate, sheet resistance 50~100 Ω, TCR < -50 × 10-6/ DEG C.The pellet resistance manufactured using tantalum nitride membrane Self-passivation, the protective oxide layer on resistance unit surface protects it from will appear failure, even if moisture there are when It is also such.The integrality that TaN (tantalum nitride membrane) resistance does not depend on sealing can protect telecommunication circuit will not be because of the shadow of moisture It rings and catastrophic failure occurs.
Currently, the tantalum nitride etching method used by film resistor field is mainly dry etching, inductance coupling is generallyd use Plasma etching method is closed, F is used2、Cl2、CF4Etc. the biggish gas of risk.Such as in Chinese patent CN103700623A, Propose a kind of lithographic method of tantalum nitride characterized by comprising provide substrate, it is thin that the substrate surface forms tantalum nitride Film forms patterned photoresist layer on the tantalum nitride membrane surface;Using the patterned photoresist layer as exposure mask, to institute It states tantalum nitride membrane and carries out dry etching, form tantalum nitride layer, the radio-frequency power of the dry etch process is less than or equal to 500 Watt, the temperature of the wafer-supporting platform for bearing wafer is greater than or equal to 25 degrees Celsius.In Chinese patent CN104835908A, propose A kind of tantalum nitride lithographic method for 3D AMR characterized by comprising substrate is provided, has been sequentially depositing nickel on substrate Iron alloy layer, tantalum nitride layer and silicon nitride layer;The silicon nitride layer and tantalum nitride layer are etched using chlorine-containing gas, opened with being formed Mouthful.In Chinese patent CN104599943A, propose a kind of using CF4、SF6、Cl2Equal gases carry out tantalum nitride layer etching Method.And tantalum nitride membrane wet etching technique and corresponding etching liquid have not been reported.
Dry etching relevant device and consumptive material are monopolized by beauty, three state of Japan and Korea S. for a long time, technology blockage, equipment manufacturing cost High, production cost is high, is restricted the application of tantalum nitride membrane.Dry etching is big with equipment investment, produces It is at high cost, risk is strong, production environment requires the disadvantages of harsh.
Summary of the invention
It solves the above problems the object of the invention is that providing one kind, makes in the manufacturing process of tantalum nitride membrane resistance , for etching the etchant of tantalum nitride membrane.It can be quickly and efficiently good to tantalum nitride membrane controlling Be etched, can obtain the tantalum nitride film layer of surface flat-satin, realize wet etching photoetching process.
To achieve the goals above, the technical solution adopted by the present invention is that: a kind of etchant, the etching solution Combination is mainly the mixture of hydrofluoric acid, dodecyl alanine, Phen and water composition.
Preferably, the mass percent concentration of the hydrofluoric acid is 5-30%, the effect of hydrofluoric acid is to tantalum metal film Etching, when its mass percent be lower than 5% when, it is too slow to tantalum metal film etching speed;When higher than 30%, etching speed is mentioned Height, but the discoloration of photoresist can be caused and fallen off, tantalum nitride membrane effectively graphical photoetching cannot be completed, therefore not preferably; Preferred concentration is 10-25%, and etching speed is very fast at this time, and graphical lithographic results are clear, good resolution.
The mass percent concentration of the dodecyl alanine is 0.1-10%, and dodecyl alanine is as hydrogen Fluoric acid etches the surfactant and promotor of tantalum nitride membrane, can be adjusted reaction speed to meet by its dosage Requirement of the different clients to etching speed;In addition the use of dodecyl alanine can increase the intimate of etching solution and metal Property, improve etching solution to the affinity of photoresist, can effectively inhibit etching liquid to invade photoresist and tantalum nitride membrane faying face Erosion and infiltration.To obtain the tantalum nitride metal film wiring with surface flat-satin.Preferred concentration is 5-10%, is nitrogenized at this time The surface of tantalum metal films wiring flat-satin the most, etching speed are also able to satisfy the demand of most of clients.
The mass percent concentration of the Phen is 1-15%, and Ta can be effectively complexed in Phen3+Ion is formed Stable complex compound not only greatly increases the production efficiency to effectively improve etching speed, also can effectively avoid because of etching Speed is slow, causes photoresist to be soaked in etching solution for a long time, it will so that part photoresist is fallen off, part metals is caused to be walked The bad phenomenon of line etch effect, to greatly improve yields.Preferred concentration is 1-5%, etching speed and etching system at this time Number is best, it is ensured that the yields of production.
The dosage of water in etchant of the invention is surplus, specifically can be tap water, soft water or deionization Water, preferably deionized water.Since a large amount of ion and impurity can be generated in etching process, so to water not rigid requirement, Common tap water or soft water can use.But consider the difference of different places water quality, it is possible to cause to etching solution Composition is difficult to expect influence, and it is advantageous to deionized waters.
When preparing tantalum nitride membrane etching solution etching solution, by raw material hydrofluoric acid, dodecyl alanine, Phen and Water is squeezed into blend tank in proportion, is adequately stirred and evenly mixed, and is filtered by 0.1 μm of filter, to remove mixed liquor group Partial size is greater than 0.1 μm of foreign particle to get tantalum nitride membrane etching solution is arrived in point.
A kind of wet etching method carrying out tantalum nitride membrane using etchant, using wet etching light of the present invention The technical issues of dry etching is brought can be solved perfectly in carving method, and small without etching residue, environmental pollution, and method and step is as follows,
The selection of step 1 photoresist
It is recommended that selecting the domestic auspicious red RZJ series of positive photoresist in Suzhou.When etching tantalum nitride membrane, it is preferred to use RZJ-304, RZJ-306 or RZJ-3200 type photoresist, at low cost, effect is good, ample supply and prompt delivery.
Step 2 is cleaned and is dried
Substrate is cleaned by ultrasonic 2 ~ 3 min in cleaning agent ZQ-05, is washed with deionized water, then substrate is put in hot plate On, 1 ~ 2 min is toasted at a temperature of 100 DEG C, can thoroughly remove the impurity dust on substrate, enhances tantalum nitride layer and photoresist Binding force.
Step 3 coating
Photoresist is coated with rate appropriate with whirl coating, film thickness monitoring coats photoresist layer uniformly in 1.0 ~ 3.0um Substrate surface, film thickness are consistent.
Step 4 front baking
Substrate is put on hot plate, is toasted 90s at 100 DEG C, is solidified photoresist sufficiently.
Step 5 exposure
Under ultraviolet source, 40 ~ 45mj/cm2 of exposure power, 10 ~ 15S of time for exposure are controlled, sends out photosensitive group in photoresist Solution conversion estranged, forms soluble film layer.
Step 6 development
Develop 20 ~ 30S in developer solution, is rinsed after development with deionized water, used air filtering drying, and photoresist is exposed Be partly dissolved, formed figure.
It is baked after step 7
Substrate is put on hot plate, 2 ~ 3min is toasted at 120 DEG C, removes moisture removal, reinforces the knot of photoresist and tantalum nitride film layer With joint efforts.
Step 8 etch nitride tantalum films;
After etchant is mixed, filters to form tantalum nitride membrane etching liquid through 0.1 μm of filter, tantalum nitride membrane is carved Erosion liquid is etched at 40 ~ 45 DEG C, and etching period 70S forms required tantalum nitride resistance pattern.
Step 9 removes photoresist with dedicated stripper solution.
After step 10 is with pure water rinsing, used air filtering dries up substrate, completes the production of tantalum nitride resistive layer, into Enter follow-up producing process.
Compared with the prior art, the advantages of the present invention are as follows: the present invention proposes a kind of etching group for tantalum nitride membrane It closes object, when etching for tantalum nitride membrane, can be improved and control etching speed, and effectively inhibit the bad of photoresist layer Change, as a result, the etching face of surface flat-satin can be obtained.Prior art barrier is broken through, film resistor field is had developed The wet etching technique of middle tantalum nitride membrane.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment: the invention will be further described below.To reach target effect, the inventors of this patent are with great concentration Suitable dodecyl alanine and Phen etching nitridation is added in research, repetition test, discovery in a solution of hydrofluoric acid The etching solution of tantalum films can solve the problem of encountered in current wet etching, can be quickly and efficiently to tantalum nitride membrane Controlling is good to be etched, and the tantalum nitride film layer of surface flat-satin can be obtained.Further to each component in composition Use level completes the invention of this etchant after carrying out analysis of experiments.Etchant of the invention is characterized in its packet Contain: the mixture that hydrofluoric acid, dodecyl alanine, Phen and water form, the mass percent of the hydrofluoric acid are dense Degree is 5-30%, and the mass percent concentration of the Phen is 1-15%, the quality percentage of the dodecyl alanine Specific concentration is 0.1-10%, and the surplus is water.
(1) the etching speed measurement of tantalum nitride membrane
Sputtering film-forming tantalum nitride membrane is used on the glass substrate, and film thickness is made to reach 300nm.It is coated on tantalum nitride membrane RZJ-304 photoresist forms etch-resistant coating pattern.The substrate is immersed into etching solution shown in table 1 under the conditions of 50 DEG C of temperature 1 minute in composition, it is etched.Then it washed, be dried, after stripping photoresist, measured with scanning electron microscope (SEM) Etch quantity.
(2) the infiltration observation of the smooth surface of the etching face of tantalum nitride membrane and etch-resistant coating
Sputtering film-forming tantalum nitride membrane is used on the glass substrate, and film thickness is made to reach 300nm.It is coated on tantalum nitride membrane RZJ-304 photoresist forms etch-resistant coating pattern.By the substrate under the conditions of 50 DEG C of temperature, with calculated from rate of etch 1.5 times of lucky etching period are etched its impregnation.Then it washed, be dried, remove etch-resistant coating Afterwards, with the state of the infiltration of the smooth surface and etch-resistant coating of the etching face of scanning electron microscope (SEM) observation tantalum nitride membrane.
Table 1
M%- mass percent
⊙-zero defect
×-defective
The mass percent of unshowned deionized water is surplus in table 1.
Embodiment 1-8
From examples it can be seen that the prepared etching liquid mixture of the present invention, i.e. hydrofluoric acid, dodecyl alanine, The mixture of Phen and water has faster etching speed, effectively reduces etching period, solve because of the photoresist time It is soaked in etching solution, it will so that part photoresist is fallen off, the problem for causing part metals cabling etch effect bad;And this The phenomenon that etching speed of etching solution is relatively stable, and rough surface and etching solution will not be caused to permeate to etch-resistant coating, obtains The tantalum nitride membrane of excellent flatness, flatness, improves product yield;In addition dodecyl alanine and Phen Content, to etching speed can with suitable control, in this way by adjust etching liquid mixture in dodecyl alanine and The content of Phen meets requirement of the different customers to etching speed.
Comparative example 1-7
From comparative example it can be seen that, the etching solution without dodecyl alanine, due to the promotion of not no surfactant Effect, etching efficiency greatly reduces, and when the content of dodecyl alanine is too low, can not be effectively improved etching solution to light The affinity of photoresist causes etching solution to photoetching glue penetration, causes the tantalum nitride membrane rough surface for being not required to etching, yields drop It is low;When the usage amount of Phen is in more preferable range, etching speed can be effectively improved, when too high levels, cause etching speed That spends is unstable, leads to rough surface.
By result above it has been confirmed that etchant of the invention can be by tantalum nitride membrane controlling well and not Occur to be etched in the case where etch-resistant coating infiltration, to be efficiently obtained the metal film wiring of surface flat-satin.
A kind of wet etching method carrying out tantalum nitride membrane using etchant, referring to Fig. 1, method and step is such as Under,
The selection of step 1 photoresist
It is recommended that selecting the domestic auspicious red RZJ series of positive photoresist in Suzhou.When etching tantalum nitride membrane, it is preferred to use RZJ-304, RZJ-306 or RZJ-3200 type photoresist.
Step 2 is cleaned and is dried
Substrate is cleaned by ultrasonic 2 ~ 3 min in cleaning agent ZQ-05, is washed with deionized water, then substrate is put in hot plate On, 1 ~ 2 min is toasted at a temperature of 100 DEG C;
Step 3 coating
Photoresist is coated with rate appropriate with whirl coating, film thickness monitoring is in 1.0 ~ 3.0um.
Step 4 front baking
Substrate is put on hot plate, toasts 90s at 100 DEG C.
Step 5 exposure
Under ultraviolet source, 40 ~ 45mj/cm2 of exposure power, 10 ~ 15S of time for exposure are controlled
Step 6 development
Develop 20 ~ 30S in developer solution, is rinsed after development with deionized water, used air filtering drying.
It is baked after step 7
Substrate is put on hot plate, 2 ~ 3min is toasted at 120 DEG C.
Step 8 etch nitride tantalum films;
After etchant is mixed, filters to form tantalum nitride membrane etching liquid through 0.1 μm of filter, tantalum nitride membrane is carved Erosion liquid is etched at 40 ~ 45 DEG C, etching period 70S;
Step 9 removes photoresist with dedicated stripper solution;
After step 10 is with pure water rinsing, used air filtering dries up substrate.
The wet etching etching liquid for the tantalum nitride membrane that the present invention creates can complete nitrogen by simple photoetching process Change the graphical of tantalum films, equipment investment is small, and production cost is low, and technical process is safe and reliable, and environmental pollution is small.Break other factory of state Monopolization and technology blockage of the quotient to dry etching equipment and consumptive material, realize local production, and substitute import.To promote tantalum nitride The marketization application of film resistor, does one's bit for the fast development of National Electrical information technology.
The wet etching method of a kind of etchant provided by the present invention and its tantalum nitride membrane is carried out above Exhaustive presentation, used herein a specific example illustrates the principle and implementation of the invention, above embodiments Explanation be merely used to help understand method and its core concept of the invention;At the same time, for those skilled in the art, According to the thought of the present invention, there will be changes in the specific implementation manner and application range, to change of the invention and changes Into that will be possible, without exceeding accessory claim defined conception and scope, in conclusion the content of the present specification be not It is interpreted as limitation of the present invention.

Claims (10)

1. a kind of etchant, it is characterised in that: the etching solution combination is mainly hydrofluoric acid, dodecylamino third The mixture of acid, Phen and water composition.
2. a kind of etchant according to claim 1, it is characterised in that: the mass percent of the hydrofluoric acid is dense Degree is 5-30%, and the mass percent concentration of the Phen is 1-15%, the quality percentage of the dodecyl alanine Specific concentration is 0.1-10%, and the surplus is water.
3. a kind of etchant according to claim 1 or 2, it is characterised in that: the quality percentage of the hydrofluoric acid It is 10-25% than preferred concentration;The mass percent preferred concentration of the Phen is 1-5%;The dodecylamino third The mass percent preferred concentration of acid is 5-10%;The water is deionized water.
4. a kind of etchant according to claim 1 or 2, it is characterised in that: production tantalum nitride membrane etching solution Method is as follows, after raw material hydrofluoric acid, dodecyl alanine, Phen and water are adequately stirred and evenly mixed in proportion, warp 0.1 μm of filter filtering, can be obtained tantalum nitride membrane etching solution.
5. a kind of wet etching method for being carried out tantalum nitride membrane using etchant described in claim 1, feature are existed In: method and step is as follows,
Step 1 selects photoresist;
Substrate is cleaned in cleaning agent and is dried on hot plate by step 2;
Step 3 coats photoresist with whirl coating;
Step 4 substrate is put in front baking on hot plate;
Then step 5 exposes under ultraviolet source;
Step 6 is developed in developer solution;
Step 7 is roasting after substrate is put on hot plate;
Step 8 etch nitride tantalum films;
After etchant is mixed, filters to form tantalum nitride membrane etching liquid through 0.1 μm of filter, tantalum nitride membrane is carved Erosion liquid is etched at 40 ~ 45 DEG C, etching period 70S;
Step 9 removes photoresist with dedicated stripper solution;
After step 10 is with pure water rinsing, used air filtering dries up substrate.
6. a kind of wet etching method of tantalum nitride membrane according to claim 5, it is characterised in that: in step 1, photoetching Glue selects the auspicious red RZJ series of positive photoresist in Suzhou, model RZJ-304, RZJ-306 or RZJ-3200 type.
7. a kind of wet etching method of tantalum nitride membrane according to claim 5, it is characterised in that: in step 2, cleaning When, substrate is cleaned by ultrasonic 2 ~ 3 min in cleaning agent, is washed with deionized water, then substrate is put on hot plate, 1 ~ 2 min is toasted at a temperature of 100 DEG C.
8. a kind of wet etching method of tantalum nitride membrane according to claim 5, it is characterised in that: in step 3, carry out When coating, photoresist film thickness monitoring is in 1.0 ~ 3.0um.
9. a kind of wet etching method of tantalum nitride membrane according to claim 5, it is characterised in that: in step 5, carry out When ultraviolet source exposes, 40 ~ 45mj/cm of exposure power is controlled2, 10 ~ 15S of time for exposure.
10. a kind of wet etching method of tantalum nitride membrane according to claim 5, it is characterised in that: in step 6, carry out When development, develop 20 ~ 30S in developer solution, is rinsed after development with deionized water, used air filtering drying.
CN201811099131.4A 2018-09-20 2018-09-20 A kind of wet etching method of etchant and its tantalum nitride membrane Pending CN109111925A (en)

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