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1. AGENCY USE ONfY (Leo . e blink) T. REPORT oAtf 3. REPORT T, ATYP OATS COVERE,1 6/10/96IFinal, 9/29/92 - 9/30/95A. TI•LE ANO SUBTITLE A study of Diamond & Diamond-Like S. fUNDING NUMBERS

Thin Films with Applications to Large CaliberElectric Guns & Associated Energy Storage Devices DAAA21-92-C-0080(Capacitors and Bal e ie )

Dr. Elvira Williams, P.I.

A t;:.~A 0 , N: t 4 A t.o (5) 0,;) A[tfl•. 5 ) 6. b L'" ot S S f2 l O 'NorlW~i'th Carolina Agricultural and Technical StateUniversity

1601 East Market Street 4-41065Suite 305 Dowdy BuildingGreensboro, North Carolina 274119. SPOCSORINGMNtONITORINc, AGENCY NAME[(S) AND AOODR1SStS: 10.A SPONSORING/MONITORING

AGENCY REPORT NUMBER

Department of ArmyU.S. Army AMCCOM UnknownPicatinny Arsenal, NJ07806- 5000

11 SUP?LfmfHTARY N~OTES

___19980203 051N/A

Un I i m i ted CQUALITY I-sIA~w.ýIz 4

13 48~l,•,IR {gA ,,CT.dO •-, ..

An interdisciplinary research team of A&T Physics and Chemistry facultyand students ( graduate and undergraduate) successfully deposited thindiamond-like cardon (DLC) films on substrates provided them by ARDEC,.s proposed. The substrates included aluminum, alumina, copper and-opper chromium. The films were grown by the Plasma Enhanced Chemicalapor Deposition (PECVD) method using a deposition system by Technics,

Inc. The films were characterized by their indices of refractionmeasured using a Gaertner L - 117 ellipsometer) and their Ramanpectra (measured using a spectrometer at the University of North

ýarolina at Chapel Hill, Chapel Hill,NC). Graduate studies ( I M.S.,I Ph.D.) dissertations were developed from this study. The M.S. thesiswas completed by and A&T Chemistry student by the close of this project.Important dielectric studies were done by the Ph.D. graduate studentat the Institute of Advanced Technology at the Unversity of Texas atAustin, Austin, TX.

1 S . N Uh t,XU LR ( 1r ,(,u92 1including

diamond thin films, diamond-like carbon (DLC) thin 2 e"4-c--es--films, dielectric properties/applications N/A

II SICURJTY ((ASS;4(A ow 8 Si UIiY (LA Vll.>. TI'- 1 ACUiY (A' ( p 7C' 20 I lION Of ASIkT A-f' TOF R[POAT Of ftiiS PAGI_ Of AW TIkACT

unclassified unclassified unclassified

North Carolina Agricultural and Technical State UniversityGreensboro, North Carolina

"A Study of Diamond and Diamond-Like Thin Films withApplications to Large Caliber Electric Guns and Associated

Energy Storage Devices (Capacitors and Batteries)"Contract No. DAAA21-92-C-0080

Final Technical Progress Report(October 1, 1992 - September 30, 1995)

prepared for

United States ArmyArmament Research Development and Engineering Center

(ARDEC)

submitted by

Dr. Elvira S. Williams, Principal InvestigatorDr, Johnnie Richardson, Jr., Co-Investigator

Dr. Alvin Kennedy, Co-Investigator

October 26, 1995

Approved for public release:distribution unlimited.

M

TABLE OF CONTENTS

DESCRIPTION PAGE

I. Final Technical Accomplishments Summary .................. 1

II. Planned Technical Accomplishment Summary .......... 14

111. Final Financial Statement ............. .......................... 16

I. FINAL TECHNICAL ACCOMPLISHMENTS SUMMARY

1. First Quarterly Technical Report (October 1, 1992 - January

26,1993) Summary - Year 1

During the first quarter, the project was staffed with a principal

investigator (physicist), two* co-investigators (1 physicist, I chemist), a

part-time secretary, one graduate student (chemistry) and twelve (12)

undergraduate (physics and chemistry) student workers. [Note: Budget

revisions made by ARDEC, reflected a $3,187 cut In secretarial services, but

a net $7,846 Increase in overall proposed first cycle funding, which theInvestigators were authorized by ARDEC to expend as they saw fit. The

choice was made to use the net increase for the first funding cycle forstudent workers]. Also during the first quarter, lab supplies were ordered,

new staff was trained and Investigators began work on the proposed tasksset forth In Appendix A, which were originally scheduled to begin in May

,1993. Also during this quarter, on January 11, 1993 tile principalinvestigator and both co- Investigators met In a collaborative conference

with Marilyn Freeman (ARDEC Contracting Officer's Representative andresearcher at both the Institute of Advanced Technology (IAT) nt tiheUniversity of Texas at Austin; and at the Electrical Armament Division of

ARDEC) at N.C. A&T State University. Together they generated a more

realistic task schedule that took Into consideration the time the awardwas actually made which was later than expected. The revised task

schedule Is Appendix B.

* One co-investigator was placed on staff in October at the beginning of the

project. Tile second was formally added In January, 1993 at the beginning of

* the second semester, because his department (Chemistry) was unable to find

replacement teaching staff for his classes (which began in August) In October.-1-

2. Second Quarterly Technical Report (January 27, 1993 - April 26, 1993)

Summary - Year 1

During the second quarter, the N.C. A&T State University research team

members concentrated on characterization of the deposition chamber

(See Appendices C and D) the x-,y-,z- directions for diamond deposition

using silicon substrates as standard, as was proposed. They found that

deposition depended on x-,y-,z-. Note: The chemistry members used

Infrared spectroscopy to characterize the diamond and diamond-like carbon

(DI4 C) filmns.

The physics team members deposited and characterized the films. Asproposed, they deposited the films using the Plasma Enhanced Chemical

Vapor Deposition (PECVD) technique in their Plasma Deposition Chamberby Technics, Inc. Also, as proposed, they characterized the films

using a Gaertner L- 117 ellipsometer to measure their of Indices of

refraction.

3. Third Quarterly Technical Report (April 27, 1993- July 26, 1993)

Summary - Year 1

During the third quarter, the N.C. A&T State University research team

members continued to focus on characterization of the deposition chamber

in the x-,y-,z- directions for diamond deposition using silicon substrates, asstandard. Investigations of the variation in -z gave rise to some very

interesting fringe and deposition patterns associated with spacer type andwith electric field effects which the team began to consider. Also, as

proposed, the team deposited a DLC film on an aluminum substrate

provided by ARDEC (designated as Experiment # 1, see Appendix E for

experimental detail). This deposit was made during a collaborative research

visit by Marilyn Freeman to N.C. A&T State University in June of that year.

This sample was taken back by Marilyn Freeman to IAT for adhesion studies

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and other observations. It was later brought to a Collaborative Conference

at ARDEC in June with Kern Strickland and Greg Pappatrefon of ARDEC

and the A&T research team. Here it was determined that cleaner film

handling procedures prior to deposition were needed. Also at the ARDEC

meeting were: Dr. T. Richard Jow, Research Physical Scientist at Fort

Monmouth, N.J. and Dr. W.J. Sergeant, James Clerk Maxwell Professor of

the State University of New York at. Buiffalo. Other accomplishnlents at the

ARDEC meeting included reports on: 1) the contract status and recent

visit to A&T by Marilyn Freeman, 2) technical accomplishments to date and

chamber characterization results by Elvira Williams, 3) IR analysis of DLC

films to date by Alvin Kennedy and 4) analytical tools or techniques required

for flhn characterization and desired equipment list by Johnnie Richardson.

A discussion/ planning session was also held in which It was decided we

needed to: 1) design some experiments to fill In the gaps/holes In chamber

characterization data, 2) design some experiments to get the most mileage

per experiment, 3) design multiple experiments to study a single film

characteristic, 4) establish a cleaning procedure, 5) establish mechanical

testing procedures 6) use witness plates to determine deposited mass, 7) do

reliability measurements and 8) reschedule current tasks to accommodate

new and revised tasks. Upon their return to A&T, team members completed

#1 above and either continued or began working on #'s 2,3,4, and 5.

4. Fourth Quarterly Technical Progress Report (July 27, 1993 - October

26, 1993) Summary - Year 1

During the fourth quarter, focus was on the following:

(1) continued chamber characterization. (It was determined that the

deposition process was affected by all substrate positions, -x ,-y and -z).

-3-

(2) designing experiments to get the most mileage per experiment,

A collaborative research meeting was held at N.C, A&T State University on

September 24-26, 1993. Attendees at the meeting on September 24,1993

were: The A&T research team (Drs. Alvin Kennedy, Johnnie

Richardson and Elvlra Williams), Marilyn Freeman and Dr. Persad

Chadee from the Institute of Advanced Technology (IAT) at the University

of Texas at Austin. Attendees on September 25, 1993 were: Marilyn

Freeman, Elvira Williams, Dawn Fant, and Donald Anderson (Chemistry

grad students), A. Akpan (lab assistant). Attendees on September 26,

1993 were: Marilyn Freeman, Alvin Kennedy, Elvira Williams, Dawn Fant,

Donald Anderson, and A. Akpan. During the technical meeting onSeptember 24, 1993, Dr. Chadee suggested a most-mileage experiment

in which substrate type and x-,-y, and -z positions were to be varied in a

single run (See Appendix F. p.4 for description of experiment).

(3) establishing a routine substrate cleaning procedure (acetone bath)

on all substrates and an etching procedure (using NaOH solution onselected aluminum sui)strates)

(4) deposition of DLC llmis on alunfiuinm (to replicate the results of

Experiment # 1 - reported on In the third quarterly report- but this tine

with cleaned substrates). Also, deposition of DLC films on copper and

copper/chromium substrates provided by ARDEC was a focus.

The purposes of these experiments (See Appendix F, pp. 5-27 forexperimental detail) were to: obtain preliminary temperature profiles

using heat tapes, replicate results of Experimnents# 1 with cleaned

substrates, obtain samples of DLC films for further analysis by test

methods other than those currently available at NC A&T, coat with DLCflhn a Cu/Cr coated ARDEC plate, and determine effects of raising Rf

power on quality and characteristics of carbon flhn (DLC) on various

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substrates,

A normalized deposition rate (NDR) was defined In connection with

variation of deposition rate with Rf power and height (z) inside the

chamber. NDR was defined as mass/area* time.

Experimental results suggests: (1) The deposition composition Is strongly

dependent upon the power, H-igh power levels (120 W) tends to produce

more graphite-like carbon structures. (2) Tile deposition rate is strongly

dependent on the power, and increases as the power increases. (3) The

deposition rate appears to decrease as the height of the substrate in the

chamber increases. (4) The type of substrate and spacer used seems to

affect the deposition rate.

(5) Electric Field approximations at film surface for metal and glass

spacers. See Appendix F, pp. 28 - 39 for discussion. Preliminary

modeling of the electric field between the plates of a parallel plate

capacitor (representations of tile deposition chamber) suggests:

(1) The localized electric field above a substrate on glass or metal

spacers predominates. (2) Inside the chamber plates, vacuum, spacers,

substrates, DLC films, all iror a series capacitor arrangement. (3) The

top capacitor plate Is at 440 volts.

(6) thickness measurements of DLC films on silicon wafers/glass

substrates. These analyses were made by Marilyn Freeman at sites other

than A&T. Such measurements (using a Dektak IIA surface profile

measuring system) revealed that our films were from 3500 to 7400

angstroms thick.

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5. First Quarterly Technical Report (October 27, 1993 - January 26, 1994)

Summary - Year 2

On December 13, 1993, a collaborative research meeting was held at Pic-

atinny Arsenal in the Nuclear Division. Attendees: Alvin Kenny, Johnnie

Richardson, Jr. and ElvIra Williams, Marilyn Freeman and Greg Pappa-

trefon. Major shared observations were (1) that deposition results

depended on whether spacers were conductors or Insulators and (2)

it was unclear whether the top or bottom plate of the deposition chamber

was at ground (the manual did not specify). The team designed some

experiments to shed light on these issues. The experiments were

to be carried out at A&T with Marilyn Free participating In the experi-

ments. The experiments were conducted.

Also while at Picatinny, the team toured Greg's lab and had some profit-

ometer measurements done on some of our flhns and found their

thicknesses reasonable. The team also toured the Optics Division at

Picatinny to try to get some Raman measurements on the fihins, but they

were too thin to yield usable results by the method used.

While In New Jersey (on December 14, 1993), the team also toured the

Electronics section of Dr. Richard Jow's lab at Fort Monmouth. Dr. Jow

agreed to make needed capacitor measurements for the team. The teani

also toured the Diamond Deposition lab at Fort Monmouth.

When the A&T segment of the team arrived back home, they did thegrounding test exl)erhnent. The grounding experimncnts consisted of

measuring the voltage versus power between the chamber plates which

showed an increase of voltage with power. From these experiments, it

was determined that the bottom plate was at ground.

A collaborative research meeting was held at A&T December 17-18, 1993

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with attendees: Alvin Kennedy, Johnnie Richardson, Jr., Elvira Williams,

Marilyn Freeman and Mr. A. Akpan (research assistant). The team carriedout the experiment that was designed at the Picatinny meeting to

determine the effects of grounding the metal substrates oil the quality

and characteristics of deposited carbon films (DLC). This experiment was

labeled Experiment #4, since It was the 4th experiment that the team did

together. The details of this experiment are in Appendix G.

Experimental results suggest: (1) At 30 W, the substrates which were In

contact with the baseplate have a higher deposition rate than the

substrates on insulating glass spacers. (2) For both types of spacers, the

deposition rate decreases as the height increases. (3) At 90 W no uniform

film was deposited on the substrates in contact with the baseplates. There

appeared to be remains of etched film on the surface of these substrates.

The deposition rate for these films were calculated from tile debris on Mle

surface. It Is possible that a film was formed, but tile etch rate exceeded

the deposition rate for these conditions. At any rate, these results clearly

demonstrate that the electric field near the surface of the substrate

strongly influences the DLC formation. (4) The surface of grounded

substrates (1 Cu, 1 Al) were etched away, while the surfaces of floating

electrodes ( I Cti, I Al ) were coated with lilorm I)I,C lh11is. The

substrates were all In the chamber at the same time and part of tile same

run. Under these depositlon conditiios, the Cti mid tihc Al depositlOils

rates were the same, while In previous experiments, the Cu deposition

rates were lower than those for Al. The differences could be due to the

different local electric fields for the two experiments. (5) For Cu sub-

strates on glass spacers, there appears to be a linear relationship between

power and deposition rate.

The complexity of the deposition conditions needed for DLC filmsrequired that we begin to consider using experimental design techniques

to determine the Important deposition factors.

-7-

6. Second Quarterly Technical Rteport (January 27, 1994 - April 26, 1994)

Summary - Year 2

Aside from weekly seminars with faculty and students to discuss and

plan project events, the following other technical accomplishments were

made:

1. Fabrication of 2 working AI-DLC capacitors (Al coatings done at

ARDEC, DLC coatings done at A&T). Capacitors gave dielectric data,

although they did show signs of leakage, possibly due to pinholes.

2. Made null Raman readings of selected films (made at A&T) at ARDEC.

Readings possibly null because the films were too thin.

3. Began to compile a data base of all runs done at A&T to date to look

for patterns and other information that could enhance deposition

techniques.

4, TEM measurements on DLC samples (DLC deposited at A&T, TEM

measurements made at the IAT). Ring and spot patterns found suggest-

ed crystalline film components. X-ray diffraction patterns suggested

amorphous film which could be related to grain size.

5. We studied closely a paper, "Towards a General Concept of Diamond

Chemical Vapor Deposition" by Backmon and others, as It relates to our

work. A Diamond and non-diamond growth region based on the ratio of

atoms of hydrogen (or oxygen) to the total number of reactant gas atoms.

For our 22.7 sccm CH4 to 50 sccm H2 DLC films, our ratio was

calculated to be 0.894 as follows:

(90.8 + 100) sccm/(22.7 + 190.8) scem = 0.894.

We examined the capability of our deposition system as it relates

to duplicating the reactant gas ratios discussed in that paper.

6. We compiled a list of Diamond Thin Films Journals.

-8-

7. We held technical meetings at A&T (March 15-16, 1994) In which

experiments #5 and #6 were performed. The objectives of these

experiments were to obtain thicker lmns than those previously deposited

on Al-on-glass plates, make capacitor devices from them and

to analyze the devices. The experimental procedures are In Appendix H.

7. Third Quarterly Technical Report (April 27, 1994 - July 26, 1994)

Summary - Year 2 "

Aside from the sharing of technical information and updates at the

Investigators' meetings and staff seminars, very little technical accom-

plishment In the area of film deposition was made. This was because of a

breakdown of the flow controllers on the deposition system and the long

subsequent delay in the manufacturer's shipment of the new flow meters

and accessories that were ordered.

The new flow meters are calibrated to accommodate a single type reactant

gas. This eliminated tile need to calibrate tile multi-gas flow

controllers of the old system each time a new reactant gas Is used.

The replacement parts were delivered Jily 21, 1994 Just four days be-fore the close of the current reporting period. This dilemma caused

us to have to cut one of our two physics professors from the staff for the

month of July. also in May, with the close of the academic year, the num-

ber of student workers was cut from 12 to 2 (1 graduate and 1 undergrad-

uate). Graduate student, Dawn Fant (Chemistry), began to clearly deflne

a thesis problem, which was reported on in subsequent quarterly reports.

Because of the flow meter problem, a planned technical meeting between

A&T and Marilyn Freeman of IAT/ARDEC originally set for July I I-15,

1994 was cut to July 11-13, 1994. Instead of doing experiments,

-9-

Investigators at this meeting, shared technical Information and plannedfuture events. It was decided In that meeting that a no-cost extension

request should be made In order for it to be possible for the team to have

time to to fulfill original /revised contractual obligations to ARDEC. The

specific planned technical accomplishments that came out of the July

technical meeting that will fulfill all original/revised contractual

obligations were reported In the Planned Technical Accomplishments

section of the July 26, 1994 Quarterly Report. This section of the report

is reproduced here as Appendix I and consisted of a total of 12 more

experinents.

8. Fourth Quarterly Technical Report (July 27, 1994 - October 26, 1994)

Summary - Year 2

Principal investigators, Elvira Williams and Johnnie Richardson, alongwith one graduate and one undergraduate student, continued to hold

weekly seminars and to work on the project during the summer of this

reporting period.

Very little technical advancement was made during this reporting

period because the vacuum pump failed. Delays associated with thisfailure, along with those associated the gas flow controllers (reported oil

In the previous quarterly report) made it necessary to request a no-costextension of the project from September 30, 1994 to March 30, 1995.We made the request. It was granted. But, because no additional fundswere received, the staff had to be cut. However, all three A&T professors

continued to work on the project. The professors were released from theirfrom their normal duties 16% (Richardson), 2% (Williams) and 0%

(Kenny). Also, 1 undergraduate and 1 graduate student continued to bepaid from ARDEC funds. Four (4) PENS (undergraduate) students also

worked on the project, but were paid from non-ARDEC funds.

-10-

Mrs. Freeman met at A&T for another In the series of teclnilcal mect Ings

on the projects. During this meeting (October 24-25. 1994) successful

deposition runs were made on the 12 remaining experiments since the

problems with the flow meters and with the vacuum pump had been

solved.

Graduate student's (Dawn Fant - Chemistry) Ilhesis work continited,

with dctalled 1)roglcss reports i•(ade III each (lttardcrly reCporl.

9. First Quarterly Teclnical Report (October 27, 1994 - January 26, 1995)

Summary - Year 3

The principal Investigators and students continued to hold weekly

seminars and to work on the project. We continued to hold technical

meetings between A&T and Marilyn Freeman of IAT/ARDEC during

which we worked on the remaining ARDEC experinments. During this

reporting period these meetings were held December 11-16, 1994 and

January, 14-16, 1995.

Near the end of the lastý reporting period, the A&T segment of the team

began a collaborative research effort with researchers in the Physics (Dr.

Laurie McNeil) and Chiemistry (Dr, Eugene Irene) departments at the

University of North Carolina at Chapel Hill, Chapel Hill, NC. The A&T

team began traveling to the University of North Carolina (about 50 miles

away) where they spent Monday mornings obtaining Ramnan spectra of

the DLC films produced in their lab at A&T. This work was done in Dr.

Laurie McNeil's spectroscopy lab.

To increase productivity (i.e.to reduce down time in the lab) and,

therefore, to make the lab more competitive In generating funds for

continued operation, the following pieces of equipment were ordered:

-11-

1. Rotary Vane Vacuum Pump

2. Helium Neon Laser

3. Power Supply for Laser

4. Mac Performa 475 Computer System & Ethernet Transceiver

The graduate student's (Dawn Fant - Chemistry) thesis work continued,

with detailed progress reports made in each quarterly report.

10. Second Quarterly Technical Report (January 27, 1995 - April 26,

1995) Summary -Year 3

The principal Investigators and students continued to hold weekly

seminars and to work on the project. We also continued our collabo-

rative research efforts with the University of North Carolina at Chapel

Hill.

The equipment that was ordered during the last quarterly reporting

period was received and installed, as needed. However, delays associated

with equipment failures (previously discussed) necessitated a request

for another no-cost extension (from March 30, 1995 - June 30, 1995).

The request was granted.

Graduate student's (Dawn ATSU Chemistry) thesis work continued,

with detailed progress reports made in each quarterly report.

11. Third Quarterly Technical Report (April 27, 1995 - July 26, 1995)

Summary - Year 3

The principal investigators and students continued to hold weekly

seminars and to work on the project. We also continued our collabo-

-12-

rative research efforts with the University of North Carolina at Chapel

Hill.

We continued to have technical meetings between A&T and Marilyn

Freeman of IAT/ARDEC. During this reporting period, Marilyn Freeman

was at A&T May 8-9, 1995. During that time, Marilyn conducted Raman

spectroscopy experiments on some DLC samples at tile University of

North Carolina. Essentially, all necessary ARDEC experiments have been

completed at the time of this report.

In addition, to the graduate work related to tile ARDEC project that has

been taking place at A&T, Marilyn Freeman has been working on work

towards a Ph. D. in Mechanical Engineering at the University of Texas at

Austin.

In order help with the upgrade of our lab, ARDEC has donated some

badly-needed, clean room equipment to A&T (see following page for list)

for use in the Plasma Deposition Lab. However, some procurement

problems have prohibited us from receiving the equipment as part of the

existing contract, which ARDEC agreed to do. However, to allow time for

this to happen, we requested and was granted a no-cost extension from

June 30, 1995 - September 30, 1995.

12. Fourth Quarterly Technical Report (July 27, 1995 - October 26, 1995)

Summary - Year 3

The principal investigators and students continued to work in the

lab with concentration mainly on maximum mileage experiments. The

graduate student in Chemistry ( Dawn Fant) at A&T and Mrs.

Freeman (at IAT) continued to work on their thesis problems.

-13-

During this reporting period, Ms. Fant completed tile requirements for

her master's degree In chemistry and enrolled in graduate school to

work on her Ph. D. at the University of North Carolina at Chapel this

fall. A copy of tile abstract of her thesis entitled "Characterization of

Diamond-Like Carbon Films Using Two-Level Factorial Experimental

Design" , Is on the following page. Dawn successfully defended her

thesis on August 21, 1995.

Although we have not yet received the equipment donated by ARDEC,

we are continuing to make efforts toward that end.

II. PLANNED TECHNICAL ACCOMPLISHMENTS SUMMARY

Working on the ARDEC project has been a richly, rewarding experience

for the A&T faculty and students. We greatly appreciate the support

that has be been given to us. We plan to continue to operate the Plasma

Deposition Laboratory, but with greater productivity because of the

help that we have received from ARDEC.

We will continue to watch for Broad Agency and other announcements

from ARDEC and plan to submit competitive proposals for projects that

are of mutual Interest to ARDEC and the principal Investigators of the

A&T Plasma Deposition Laboratory.

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DEFENSEDepartment of Chemnistry

North Carolina Agricultural and Technical State University

cHARACTERIZATiON OF DIAMOND LIKE CARBON FILMS USING TWO LEVELFACTORIAL EXPERIMENTAL DESIGN

By

Dawn Ifeather Fant

There are many chemical vapor deposition (cvd) techniques that have been used tosynthesize diamond and diamond like carbon films. These different cvd techniques have allproven to effectively produce diamond and dic films. However, some properties such as filmquality, growth rates, and thicknesses vary from technique to technique. Very little is known aboutthe actual chemistry involved in the cvd system and as a result there has been an on going quest tooptzie tie different deposition systems. There has been a tremendous amount of work done todetermine the best processing parameters for the synthesis of these films for many yeats.

This research focused on using the first level of a two level factorial design tochartcterize a radio frequency plasma enhanced chemical vapor deposition system. ExperimentalDesign is a statistical mathematical model that is most often used in chemical and engineeringplants to optimize chemical and manufacturing processes. This model reduces the amount ofexperiments needed to gather a sufficient amount of information, determines importantexperimenltal factors and the effects that varying factors simultaneously has on the system.Substrates were placed synmmetrically in four posi*tions in the deposition chamber. RF power wasvaried between 30 and 155 watts, substrate heights were varied using glass spacers between 0 and7 mm and gas flow rate ratios were varied between 25 and 45% CI-14 - H2ratios. The films werecharacterized using mass determination, profilometry, ellipsometry and FTIR. Thesecharacterization techniques were used to determine the important main and interaction effectsassociated with dic film deposition.

MONDAY, AUGUST 21, 199512:00 PM

ROOM 101, IIINES IALL

--15--

III. FINAL FINANCIAL STATEMENT (For months ending July,

August and September, 1995)*

1) STUDENT WAGES ........................................................ 50,976.00

Amt. Encumbered/ Date

Spent: 50,971.00 9/30/95 Balance: 5.00

2) LAB SUPPLIES .............................................................. 22,531.00


Spent: 22,523.00 9/30/95 Balance: 8.00

3) OFFICE SUPPLIES ............................................................ 283.00


Spent: 281.00 9/30/95 Balance:

2.00

4) OFFICE EQUIPMENT ....................................................... 760.00


Spent: 753.00 9/30/95 Balance: 7.00

5) SCIENTIFIC EQUIP ...................................................... 12,635.00


Spent: 12,628.00 9/30/95 Balance: 7.00

6) TRAVEL ....................................................................... 8,735.00


Spent: 8,443 9/30/95 Balance: 292

* Expenditure and balance entries are from P. I. records, except where

indicated from attached University Records

-16-

Financial Statement (cont.)

for months ending July, August, September, 1995

7) MAINTENANCE ................................................................. 0.00

Amt. Encumbered/ Date (3,000 transferred)

Spent: 0 9/30/95 Balance: 0.00

8) EPA SALARIES ...................................................... 138,640.00


Spent: 138,640.00 9/30/95 Balance: 0.00

9) FRINGES ....................................... ...... ...... 33,274.00


Spent: - 9/30/95 Balance: 10,738.94

(University Records)

10) INDIRECT COSTS ................. ........ 107,182.00


Spent: - 9/30/95 Balance: 15,252.41

(University Records)

Total Contract Period: September 29, 1992 to September 30, 1995

Total Contract Amount: $378,271

Funding to Date: $378,271

-17-

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AP&"PENDICES

Appendix A

Proposed First-Year Task Schedule

PAppendix AProposed First-Year Task Schedule

Charactelize Our ChaMber May 1992 Jun 1992Coat Flat Glass Samples Jun 1992 ull 19 q-.2Charactetize Glass Samuples Jul 1992 Aug 1992

Coat Aluminum/Alummia Aug 1992 Sep 1992

01 Glass Samrples

Chai actetize Aluminum/Alumtia Sep 1992 ( 9)c I1) 9

Samples

Coal Flat Copper Samples Oct 1992 Nov 1992

Characterize Copper Samples Nov (992 () c 1992Coat Flat Conrposiles/Polyfiides Jan 1993 Feb 1993

Characleulzte Copl)osileslPolymkies Feb 1993 Mar 199:3

Coal Flat Metals Other 1 han Copper Mar 1993 Apir 1 99•Characterize Metal Samples Apr 1993 Mviay 199:3

Appendix B

Revised First-Year rask Schedule

Aiiendix B3Revised First-Year Task Schedule

Trhe principal in1vestigator mid both co-dil-ectol-s miet xith Mrs. Mailyn11 F)eCC-rnali, Contracuting Office Representative, at North Ca-rollina A&J* State Univer-sityon 1 I Janiuay 93 anid together generated the fbllowizig rev'ised techmiicai plaiiwhiich represents a. more realistic scheme consider hig Lthe time the award wasmade (near flie end of the Fall Seimester):

PROCEJJUU.E LJA'1

Characterize Deposition Chamber (x,y~z January - May, 1993opthtrrLzatlon; coat silicon xvafiers usingcheincore or mixcroscope glass sp~acers)

Characterize Filmns on S1licon January - May. 1993-1'lllcim~ess (weight averages. tally

surfaces, iriterft~rerce)- Index of Refractoio (ellipsonictry)- Composition (FTIA.R., Auger(?

X-ray dilfractlorm)- Adherence (plasina cleaninlg to anssist- lail. E~ffect

Review (COP and'resea-rchers meretingi May. 1993- Exanihie Data- Examine Charts/graphs (describing

experiments and tesults)- Strategize (based 01n reMslt)

Coat, Aeon Glas's Samnples June-August. 1993Clmaxacterxize FlIlms (anjd glass)

coat "AIYA 3 on glass samnples

Cliaracterize F1111s (anld g~lass)

Review (Con amid Resea-rchers Meccing) August. 1993- E~xamine Data- Exandrie Char ts/G'raphsi (desqci ibimjg

experimients anid results)- Strateglze (based on results)

Beginm Coating Copper Fihrms ont Glass Septemnber. 1993

Appendix C

Schematic Diagram of Deposition Chamber

Lid C) rzl

( 1 7 )

00

U) U)

0

-A U) 0

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(aqeti 0oloa p0W~BGoj~WL-I xlpad

Appendix D

Photograph of Deposition Chamber Showing

Baseplate, Cover and Some DLC Flhns on Baseplate

Appendix DPhotograph of Deposition Chamber Showing Baseplate, Cover

and Some DLC Films on Basepiate

................. ...

Pijjj t.s~ i tnbr Si~i i ic;i 1 ~ i iir un'ii( rI j ,"J g n frIi

Appendix E

Experiment #1 (discussed under section "c" below)

Figure 13-3: |uii 1132(3-0°

Sclent-tlc Assoclatloons and Other Colla borative Elhnrts

The Inent.)ers of the Dlanuoiud-Thhi Flmnts Team at A&1'l keel)

III close contact, inot only amonlg themselves but also Xvithteani memibers at Mie University of Texas at Austhin (UT) an1tl at

Pfcahinly Arsenal. Durhig this quarter, tearn mnembers haveexeianged technical and other hilbrinatlon not onily through

telephoine confer-eices, fl-xes, wiltteii correspondence, etc., but

also through thie lIbIlowhig activities:

a. Weekly Seminars

The A&T facultly and student researchers elngagedl InWeekly techntcal seminars bi-r hiffrutatloi exchange oplics

related to the ARDEC project.

Ii. ScICnif(Ic Meetings

The 1)l-l~CiPai 1.1Ives Ilgator. elgI ii (8) uiidtergradmatc

student researchers and one il1) graduate student, natIeided

Whe Natitonal Society of' Black Phlysicists CotiiPei-iice hii

Tallahassee, Florida onl April 2 2l,199',3. , 1 11 cec (31

undergraduate studenits presenited pApers rand II irce othercs

presenlted1 posters -at that mneetinig. iFluat iiicclIig 'WaIS

subs tuthted I'or tile two (2) pIaiixied Stimmner 1 992 i met ii gs.

c. Technical. Meethig at: A&T1

MIaRilyn Frecinati ol h(li Inust ituit of Advanmcedh(I Techilogy

at tile University of Texas (UTI) at Austin cand file Eleet i len

Arnuaiiient 1)lvlsIon -at ARDEC mtet withi A&T ARL)FA. Ihutily

(EI~ivlra Wfilliams and Jolnidiie Richiardsoni Fromt tfic

Depart-ment of' Physics -and Alvin Kenniedy Rlom tile

Departnmenit of- Chenistry) rand students, Junme 16- 18, 1993.

Technilcal raccom plISinnemci ts durhig that me1eting Inlmiuded:

future project experhmnents, colitatminlltmm re )tit1 (Itt ring

processing, sharting of' technlical1 p-,pers teaod 0 tile

project anld Joint perlirill'allee of' i)r-oJct expeilimieumis (see

Fi1gure 1343) by A.&T anid UT'Team Ineuinbers.

O1ne of' these experititeim t's was designaIted E~xperiment(

IIshiliCeC It Wis (.1 c, Iir-si.jobit. A& TIIAI th alIwas9 ImIC 011

a S~bStIT-'te p rep-alced by ARL)FC.. hi Ex1 erilmmem l 111 j

DLC Mlin wa-,s plhaced oti ai-m Alunimunmi sub'str.alc p] e-

paredl by AliE>All AIZDEC-- scanmples wvere 11mimom imidi

on 7 nin high glass laes

d. Technilcal Pv'eetliig at PIc- tli y Aisenual

Thew A&T 1acnmi Ify researchers ".111d Maruflyn FcI mmnil imet

at 1'Icat.i tmiy /\tscivAl with 1(crii Str ickhrhmd nt 11( (Aik1

I'lep)CIIXCIlimi ol'f 11 Nticlecor 1)ivislu, Oi uly 1.4 -115). I 993. Also

present at [htII)CCeing Iwere: Dr. T. lMchiard low, Resc'arcl

Physical scieltist -at F'oiL NJmiiuli WIAm Dv-u I W. V.

Sergeant, Jamies Clerr Wi-~xivell, 1illeossor of, the Si ah,

Uj~ilveuslf V of'Nmw YOjik ;d. 8uiffhlo.

Prior' to the A&Tl 1FICU~ty ICSeAVCImeUs -rIl t tMIS

Inieeting, Marlyn1,1 Eeevimiam h ad 11111 tillchlimess

iiiestueimeuis iuuae at AIU)1P1C oil mne snmpulc filmu iwutlc al

A&TI duriviig, her hine titlp there.- Thi'l h~ics swo 0vu .16

umlcrons . Thle tiuickimess imceecs to be -at. le"Ast 0 .50 1muirroums.

Ms. Frceimam hadl deliberatel1y Inrot,1131 . thme l1111lummsic at

A&T to the Al D[)Jt,( in cetii g (It comp -ii ~cl, closed1 cm n'ii lit

lIn 110C xeadilwi Via skaiudaid allpoll fliggage--i hatli)j11ig

procedur-es a.3 -a wearj test. 'Vme-y were (lJ-i~edlt have

ibegtul to Sweat. atid to hak.1e nu ountd 1 lie subsi tate edgel~s.

Also adhesioni tests of' the )LC' I1lin~ oin Me glass Mol.njt. oF

the ARDEJC At substrate had beenx done biack rai. A&T utsing

acetone, kidm wipes, fingernaill and scot-ch tape. Rt passed all

of'these tests excep~t, the scotch tape.

Irjpo1 is oil: I) Ille c'oijl ut(1 st"11 tt 111l Ilie i(rcelfliVl to

iX&Cl by lla~uliyii Fi'er-imiin, 2,) teclunical. aeconip list I I Ieii to

WHilhamus, 3) JR anlsi fI) lins, lo daile 1).y Alvinl

K~ennedy, and 4) aiiaiylical tOol or- techique(LIs requIred-C Ibr1

flit llaaeerl.aiouaid esir-ed eq(Ul)ipment list by,ý Joluuuuxie

iciar-dsoxi.

igure (iC-2

Normaized Deposition Ialte vs Power

/ =1 mmB

0

* Al on Glossi Cu onGlossA Gloss0 SionAl AvV Si on Gloss

zxnLV

V

0 30 60 90 120 150 180

18owor(wa)

scans/spot) were taken at four diflereint locations on

each wafer. Each location was approximately 90(

from each other.

Flgures C-3 and C-4 shows tie i'IR spectra between

1350 and 1150 cn-' as a l1inctIoi of lheight for 30 and 120

watts respectively. All spectra have a peak at. 1440 cin"'

which corresponds to a CII' or CI-I deformation. This Is

consistent with tie termination of diamond region in tie

film by these groups.

Figures C-5 and C-6 shows time VI.'Il spectra l)et.ween

2600 and 3200 cn' as a fuincton of lelglht for 30 and 120

watts respectively. The weak spectra at 7nmn and 14nim lfor

tle 30 watt spectra are tile result of the lower tranmsnisslon

SI wafers used. All spectra display a peak near 2920 can-'

which corresponds to a CII stretch In a CI1 2 function group.

This strongly suiggests that time DLC llnis are ter•milmle d

witil Cl 12 o p)posed(l to CII( .

19

Figi~eC-3

FRR Transmisson Spectra vs Height at 30 walls'011 Asyrne tna stch

o0-

Cle

20

Figure C-4

FIR Transmison Spectra vs Height at 120 wattsCtrA Asyrnetu stretch

00-

010

21

Figure C-5

FIR Transmission Spectra vs feight ot 30 wdisCII Stretch reqion

0

0-

(o

°04

22

'i.gu-e C-G

SFfIIk Tiron irvicl Spectro vs I-Iihl o(tl 120 walLt'C I1 lretch region

• C)

00)

~0

A00.

-133

.- , d'2

23

Figures C-7, and C-8 shows the FIHR spectra between

1550 and 1800 cmni as a finction of height for 30 and 120

watts respecilvely. Figure C-8 shows strong IR peaks

between 1600 cm-' and 1650 cm-' , which Is the spectral

region where carbon double bond stretches (C=C) usnally

appear. This suggest that at lidts power more unsal.ttrated

carbon or graphite type cot1IIpost(lons a-e being rornted.

These carlbon-car.)onl double bond features are present at all

iclglhts. There is 1o idl(licati,.lo tita. sir ri1llir sIrtru.ctlt-ICS are

formed at a power of 30 watts ( Figure C-7).

3. Summary

A) The deposition composition is strongly dependent

upon the power. High power levels (120 watts)

tends to produce more graphite like carbon

structures.

B1) Tlie deposition rate Is shrongly dependent upon the

power, and Increases as the power Increases.

24

Figure C-7

F l-I[rtansmission Spectra vs I leight at 30 WattsC=C )Sretch region

0

0.ol

25

ig��e (C-8

FliR Transmission Spectra vsl-Height ati120 WattsC=C Stretch regjion

00

U,

00

26

CQ The deposiLion rate appears to decrease as the

height of the substrate In lie chamber Increases.

D) The t.ype of substrate and spacer used seems to

affect the deposition rate.

27

D. Electric Field Apto ~~dixloi t "Ki itl~eLr cu itt(1u~S~i~

1.'Vellutlilduty utodelitg of'I thre Oleeiic fi4+d iJ(tiAv.1( til pIWIteI of~ o p--1"" pit

~aptet~orIaeprecsCitatl.lsot15c 1.1 depostilolol (: 1ti,0io1lows (III tile next sevel'. pnyst'i.

satish-al.'- oil glass o1r Illutal stccwi" f (itliIc' v"wtItt111, ~pwti

DLC~ 1Blixs, -nit WWII oU7x1, ed11 .5!ul(~ ('-t 1)"leitor aw itttgeielIl. (3) the tup c~pwlu

plIate is at 440 volts.

Also' ill thjesd miodels, tile fbilowbiig symubols have been tliicd:ed

C =cnpacitwilceý

eo!- permnittivi(y of' lCre s;,cee

A ar-ea

d dlstamce betw~een capIacitor plates

U the ellewrgy

V tile voltage

It tile dielechiW, vonst-mit

[The differenlt W's teIpresetii ttie regionis of difihrlenit tile-mbl Icollti ait.t h)Ct\Vct thc

Capaclitor plIates. Iror W3iil~h iodl1ihh , .1110 awl IA h wlg lmf CI 'scil the

dielectric cotislaiit Ibor a gloss spauer. a 111slconl it~bstrne, a DL.C Hlimt mid -. vN11tmillI,

respectively. Prellitiiiiaty nuit1tellIcAl vniles thot mppi oximtutt thlose ofth diw ct c

tided hIl oUr basic iDLC expel-illetits ate exploredl lisiig 'iR Solver 111mg compititet.

soft1avf1e o gelierate iiuiiilers that call bc! compar)eWd wilthi Ice- paranmeteiT valu~es.

r~quatlotis twed lit the, above mo1dels9 1iiCIudeC

VOLUMEi = A. d

u =0 /2) CV11

U =(1 /2J( 0 J 2l (1,- voltitie

C = ItG A/d) WIC1.11

1/+ 01( 1 112)+/C + .......... eapac It oi1s hIlSCI cI en)

'Modd~~i tiIeLc tet In ihe IDepus Ho1bW (h Ibe' :Y

c !: eo+A/dU -(C+VA2)/2

'o (/)eTI(E-AZ) *vot Jumevoltiiie -- A~d

29J

St inpuA Nampe Ou Lpu Unit ComitentLC 2, 206E-12 Farads -the capaci tance

8,95E-I2 e0 coulonibssM081 A III the ir'ea of the capacitor'.0325 d III -the height of -the coaptci tot gop

U 2.1351E-7 joule440 V vol ts -the potential at -the top plate

9573.138 vol ts/mt -the electric Fieldvolune .00026325 mtcubed -the volume of the diel~ectric

30

SL JriIAL~ Ncuiie ___ L Uuwi LC 1. 741E3-11 fuoldds

1~7 k8 85E-12 eO coulunibss? .0081 A ts

.07d vIIU 1.6852E-6 joules

440 V voltsE4,4446.712 volts/rn

volume ? .0000567 iticubed

32

S. Rule'Model A3 -A parallel plate capacitor filled with"di~tectrics ki and k<2

C =(2½0O*A/d)*((kl*k(2)/(k~-l(k2))

u C'*(VA2)/z*Ul (i/2)*eO*kl1*(131A2)*VoiumeIU 2 (I/Z)*eO*k2*(E2A2)*volumueZ

*volUmiel A*dlSvolurneZ A*d2*E = atpha*EI*E = beta*E2

* LL

33 uu~.

$t J•np± Mcn.__e QuLpuL Unit CceiienLC 2. 869E-12 Farods

" ~k

8.85E-i2 eO couWcitbss

.0081 A 1sq

.0325 d IIIU 2.7771E-7 joules

440 V micubed13538 E volis/m

volume nicubed1.86 I1d1 k2

U1 9.5004E-7 joulesEl 45119.647 volts/mvolumel .0000567 micubedU2 3.4174-E-7 joulesE2 19336.445 joulesvol Lmie2 .00020655 mcubed

.007 dl m,0255 d2 m

G a30004667 alpha-7001287 be-to

34

5' Rule"IModal #4 - A oarallel plate caipacitor -filled with"t~hree dielectrics 1(1,1(2, k3

1/C) (dl/kl~eO*A) + (d2/k2*eO*A) + (d3/k(3*e0*A)*u C*(VAZ)/2* (i (i/2)+eO*kl*(EIA2)*vo'tumtel* 0 (i./Z)+eO*k2*(E2A2)*Volume2

U!2tJ (1/2)*eO*k(3*(E~3A2)*voitume3*vol umel A*dl

* volume2 A*d2'~volwnhe3 A*d3*E = alpha*E1E = be~c1*E2*~ ~ Fonun*E

*U =U1 + U2 + U3

35

St. inp~ut Nome ___u- M-Li Comntei i

C forods

1.86 Id

vol umiel micubedvol uuie mcubedvol umie3 iticubed

13538 E vot s/mt[1 67690 votts/mE2 45126. 667 vol Ls/il

E33 27076 vol Ls/m'

30 U joulesUl joulesU2 joulesU3 joules

.2 al pho.3 be La.5 goaiviuco10081 A s

.007 d l

V mcubed

dleO coulombssd2 i

d3 i

36

S M "tt'IModdl #/5 - A put'tllet pl[ate copocitioI FittLed with"*thro~e dielec trics 1(1, 1(2, (3, k4

"(1/C) (di/kl*eO*A) 4- (d2/k2Z*eO*A) +, (d3/1k3*eO*A) + (d4/k(4*e0*A)IU ==C*(VA2)/2U!1 (11Z) *e0*Id*ý(E1AZ) *Vol umelU2 (1/2)*eO*kZ*(EZA2)*volumheZU3 (I/2)*eO*1k3*(E3A2)*Voluule3(14 -(1/Z)-+e0*1k3-*(E4-A2)N*-o'uime4.

voltumel A*divolwreZ A*dZvol ume A*d3vol une4 A-*d4.

E =2 betcl*EZE =2 gaufI"O*E3E =2deitc*E4

IU= U1 +UZ +U3 +U4d = dl. + d2 + d3 +~ d4-

'37

SI: Thp_•L Nume Ou pAu L UiwLt Coonmmen

C 5. 1891E14- foro'ds,007 dc i:i

1,86 Id.8.85E-12 eO coutombss

.0081 A msq

.003 d2 i

2 1(2•.0015 d3 mZ 42 Id3

U .00003611 joulesV 3.731r-10 voltsU1 Z.1382E-6 joulesE1 67690 volts/mvolumel .0000567 mcubedUZ 4.3794E-7 joulesEZ 4.5126.667 volLs/1volume2 . 000024-3 mcubedU3 1.4-904E-7 joulesP3 3384.5 vol -s/mVolume3 .00001215 mcubed

13538 E vol Ls/rn.2 alpha.3 belca.4 gcuVuiia4021 d4 m

k4U4 3.3384E-5 joulesE4 135380 volts/mvoluuie4 .000i701 mcubed

.1 delta

.0325 d III

38

ule References For, Capocitors

"R.A. Serway, Physics For' Scientists arid ELwgreers"With Modern Physics, Third EditLio,"pp. 726 - 731

'I

"D. IHoidoy and R. Resnick, Fundcimienrols OF Physics,"it Second Edition, p. 501

"P.A. Tipler-, Physics Foir Scientists arnd Engineer's,"Third Edition, pp. 690 - 709

'I

"D.M. Trotter Jr., "Capocitors", ScientiFic Ameritcon,"IT July 1988, p. 86It

"D.K. Cheng, Fundomentois oF EngineerTing Elec tro-"if mognetics, Addison-Wesley, 1993"i pp. 116 - 142I,

"J.R. Reitz, F.J. Mltfor'd, ond R.W. Christy,"Foundotions oF ElectLromagnetic"Theory, Addison-Wesley, 1993, pp.150 - 153

39

Appendix F

Experhients #2 and #3, Maxhium Milage

Experimental Set-up, Model of Electric Field in

Deposition Chamber

Fo.u~irth~ quarter I'edmiikl I xgrcssc flellort (Eu urnlve of Sectillis C,D))

DOrtitg this rcepoititig pcilod, (Jilly 27. 1993 - (Jutoftel 263. 19931I)i

0epe11 ou-l L) cotutimped e wadei iatlIU00ti ofthe, dCej0StnsIU1I I-EIIItIhr III (IWý

7'-dilrectlot ixt dl11,110d lepOlml~ol Ont 83tIIcul substrntesI C- stamitdud ".111d

wanaysls of DIX films (See section C- below fbr dseiscssoio oftdetaiils).

(2) designifig experlmxents to get the mtost mileage per exjperbliclit. 13)

establishing a suibstrate cleaning land etching) procedure, 14) deposit-1011

,of DLC Rilms of) ahitulimm tjjcf ndCOpycr stifisti-ates provided by AIU)EC,

('151 Ele~ctric Fireld approximutions -at f(11 !3m sut ie ror metal -mid gkassý

spacefs.

I '-Teeilucict Mcceting nt A&1311vI\ I~l~ Ej~ il Decut I)'11if-d

A collaborntive research meethig was he-ld ,it NA.C A&Ti State Uitivei siy (.il

83eptember 24-263, 1993. Attetidecs cit the niectitig vii September- 241,19w3

wei-e- Tbe A&T1 research tearn (Drs. Alvin Reitmety, JUhtmlce

Itchmltaxds and Elvlra W11l1imau), Mai ltyn Preecinai mid Dr. i'er-sad

Citadee from thie lIustl(ute of[Advaniced Thehuology (INr) tit thte Utilveisity

of Texras at Austhi. Attendees on September 253, 1993 were- Marilyn

FT'eexuaul E,f!Avlrc Williams, Dawn F-atit cAnd Donald Andetrson lCheitutli-y

grad studento), A. Akpan (lab assistmnt). Attend~ees onf September 20,

i993 were- Marllyui Eteeutiwi , Alvin) JRelnedy, Elvlrn Willisutue, Valvi Fofith

Donaold Anderson, ond A. Akpsti. ittiritig thie teclmlenIO meeting Ott

September.Q4, 1993, Ii;. Chadee" suggested the most-mile1age. exper-iment

ske(.ched below!

17'-G I

slbd

III this experimenlt, glass sldes arl' to) he p~laced aVUtid the cl•mt•iler as

'1

shown fiti stacks of 1,.2,3,4 , eAc. as ft Igli as possibk fciii (the 32.5 min Ii Igh

chamber. Repent Stackithg uzifIi ll ;II(:ImtIibr baeIs Ised. PlaceSufbstnate Chips oilI each slide, stack( 811(1 IIIlfc I (Icl)OSI(foil ruthi.

Subs~trate chipsj uulay vary. e.g., Al, Cit, (cf. Mvaniy expeimenlltIs cnii be

ObtaiRICle fronit a s~hilfe rtim. F~or examp~le, dc1(1eflosilo as a finilictloii o)I

lheiglht., (iepo)(~IIO mg aI fitln(Al i of sitibstm 13ale I X'OC c. Thle A&T lenm1

p~lanls to (10 thesc xer(X)lintuils.

2. Teehniiucal Mcclin g at A&T/Subst)5 l c "Caleat ii:g and( IPI!ii gIrocchi Ic's

loft fanted

Substrate Cleaninug (amd IFtcluing):

All substrates were cleanled using best (avaflable meithiods ns follows:

Microscope Slides :Scrubbed wvith tap 18 aler am1( ci icese cloil! I Ii I('1

Finlsed with Util w-ater 811(1 Vapor driedl Ill acetonle vapor.

(Acetoxic cheicical grade)

Alumlinumu Sliect~s : Al sfiect to be coaI(cd %vas pre- po)lished~ ats-fill

t-af w'at er, ch eese clothI and "Cornilng (Claner and

tCiolld Itk)I (2r", ýa p~oflslu-liig coIpoiJ)1lid. TIlls pIate was thele

rinlsed well Ini fall Water 8111 s1ibse(Illt('itlY cleatied Nvltlu salme

uilthiod -I5 (escullled 1)Clo%%V fot rest of n~mltntiiliiii pinfe's (('()I

stacloiijJ. AXI;ll tian pulates k-vet~' 8tIh~f(*ck(I (on a I-'

hiydroxidfe soltif olot -ecfihtt1 f- 81(1lid leul ufascel Nvell fit taj

wvater. lhey wcV(ýi stI I)JII cil sedI ,1 wajIl VIi (lin) iI-ISL'lI mu1(

v~apor oIdedi Ill acctoite ~8 OS

SIj Wafers : SI mafiers were rInIsed w01it acetonle Ment 181) waler 811(1

Vapor dri-edl Ill acefotie Vapors recpentedly utitlli (l1 sie lut8cC to b~e

ARDElC Plates : P-2, B3-6), and A- 12 wei c rhised fIn tap) xvitfcr 'Ind

repleatedly vap~or cIandll acetotie V8J)ols1S 1t 1 itl te silliace to

be Coat~ed dried evenly wh~eui reialove(1 hoii thOe V8J)Org ando

"al)1earedl cleani".

3. Depvsition ofDILC FlInts oil Alti tnhit in and Copper Sn bsatrais prov'1ced

by ARDEC

Dtirhig the seconid and (fill([ days oft(w i'cecltttcai Meetinig at A&i'

(September 25-26), two exjpeilmeiciis weie peit foined (-intl 113(67 m-

E)xjerlenetL 112 and riun 1/308 or ExPAeirlmeent #13). Thew experlmtetit

perfbrined drix-ng tile )tJitl, 1993 cJliab~oratlve tcelmitial niecetlI g at.

A&T Ali(] rep~orted Wn lie ThIrd Quarterly Report Is rcfrerred to as

U.xperlinient it I1. The exp~el IIltenters for I'xperi Iieits 1/2 -and 113 were A.Akpan, 1)awi Fanit, Marilyn Freemana, and Flvir-a Willianis. Thei

objectives, anid subst-rate coidIlgurstion lin the (lepositioll cluiartber (Or

these experimenlts are sholwn below:

objective: 'r'ite turpose ofmtis expeiminltl was to obl'ailtilte ijlolohtg dahl:

1) P'reliminiary temperatture prollie uishig heat tapes

2) Replicate results of Experlimient it I with cleaned sulbsti-ates

3) Obtain samples of DLO filints For Furthter atialysis by test mtelliods. otlher thaii those currently available at N.C. A&'iSU

4) Coat with DLC illmi a. Ct1/Cr coated AR1U)iC l)Jatc

8tibstrate Coniligtrat ion lII Chamber (See top of following page)

*Note: Ms. Irxeeinat ihanded ou~t at (lils meet-ing.a r-epox I entitled, -1,lilchitess

Illensur11einellt of' Lialliolld-1lke I'ihtiu "fllns oil Siliconl Wnfieis mid U lass

Substrates", which was pextfori-ed by resatachi teami uiicuibes a atARDEC on (lie DLC filints deposited ]ii Experimnteu #/ 1.ITis report. III

Appendix C, gives lthil thilcknless 11leasuitretictiets of 3500 A , 7000) A,anid 7400 A.

18117

It/C ... Ig.... i5Itoi

2700 [9

1112 AECi se ialy niade H9 auu~ prgSl~ir~

sketc ), a hettae Iva lce u hebtouiSI

of 3M tocttehj)1atebl auiothietaoe, 10) Fof eoi siet Inth

tile stack, -auiotler oil top) of the thurd and aniother oi)

top) of I-le top slide 14) "M" lIn sketch tie-mis uii-i59 ol'toJ)

slide w-as (.akeu 'anid "T itieails a temperature tape, 1r))

Rlun fhlte was 120 juhil., ilt power was 125W and

substrate heights were all 7miiui.

Expcz-linczxt #3

Objective :To deteuuuulln effects of ralshig Rf Power oil quMality anld

characteris-Iscs of carboii filmn (l)LC) oil varjjiou~s sub~strateI~s.

7

Procedure: Substrates were clenuied using the sati)e l)roceduis us II

Experliment 2. ( StackIng slides and Al plates below the one

substrate to be coated were not recleaned and heat tapes from

previous runs were left In place since they had not changed during

previous Iui). Substrates were placed l) tile ,me collilgutril loll II

tie clhatlli.)r as In Exlrluhueult 112 amd tihe suxtc set of suri'•uit ( Al,

Si,, Mlass, C1.1 ) were tused. E1ffiurts to rel)llcatc .all depositioll

parameters of Exl)erlincit 2 were Inade except thtil f power for 11i)s

run was to be increased to 175W. I lowever, 175W was iiot

achieved, so we rau at I W75W.

Substrate ConfIgulrat.lon hiI Chamber (Sce below):

181)°

Cu/C'r conted lplite

SliA Sill le

115 '-2

hinss j111tec w/ 31ntct- Al jplaie sthil w/ widner

S lde ul• Sh ip IllOn-cl wnlere

270113 90

2 1141 113A•-ti 2 L

AI/Cgt conled phInle

Sill ic Sli1 v2

(4 sIdes)

I1-6

00°

C. Awt1Msis .ofJLCJfilis_ to Date:.

"The primary locus of these experhnlleilts was u to.(cidtmilne

the effect of both power and position of the substrate in the

depos1tion clhamber upon the deposition rate mid

composition of the PLC flhms. This section summarizes the

results of Mie depositlon ch iamber chiaracterization

experinents and prelimti-ry analysis of runs imade using

ARDEC deposliion plates. Tlie deposition rate Is reo)rtCd

usLiig a normalized deposition rate (NDR) and the cimhages hi

composItIon are reported using FIR data.

1. NormalIzed Deposition Rate INDR)

As described in a previous section the mass of each waler

was measure before and alter deposition. 13ecause ol the

differences hi the diameter of the wafers mid the deposltonm

times used these results are reported using a calculated

normalized deposition rate (NDR). The NDR pennit.s

comparlsons between difierent runs aid the formula Is

given below:

L'9

NDR- massa1cea* time

Tables C-I to C-3 show tihe NI)R For de1 )u9shilm n at.

different heights (z-direction) in thle chamber -mid different-

deposition powers. A descriptlon of tihe positloirlig of* tie

wafers can be found In section 13.

Table C-I shows Mie NDR for a substrate height. of 0 m1n1

hi tihe ciamli)er using both 30 aud 120 watts. This

correspollds to tie silicon sItjstratc rcst li g (ilicctly olt IIhe

base plate. The run nutmlber gives tie actual run number

mad Ute x,y poslil-on of I-he wafer In the chiamIbCr. F'or

exanlple It 350-0 corresponds to run 350 at x,y )oSit.lto

00. Most of the runs were taken at X,Y = 0. Two runs W11339

& #307) were made with four wafers In the chamber at four

different x,y positions (see section B lor details) at 35 watts.

Runi #370 was run wider tie same conditions at 120 watts.

Thle average NDR at Z=0mm and 35 watts power was

measured to be 3.9(0.2)E-06 ing/nmn7--mln. NDR values fbr

10

Table C-1

Normalized DeposiLion RaLe for Z=0

RUN if Diamneter Rf 'i'ime Mass NDI,_ _(tutu) (watts) (rain) (1ig) (mng/nnam2 mill)

339-0 101.6 35 360 1. 1. 05 4.01--()6

339-90 101.6 35 360 1"1.44 3.9E-0J6

339-180 101.6 35 360 11.69 4.OE-06

339-270 101.6 35 360 12.2 4.2E-06

307-0 101.6 35 180 4.89 3.8E-06

307-90 101.6 35 180 5.92 4.1E-06

307-180 101.6 35 180 5.32 3.6.E-06

307-270 101.6 35 1880 5.3 3.6E-06

,avg. = 3.8(0.5)3-{}6

370-0 .101.6 120 168 9.741 7.213-116

370-90 101.6 120 '168 9.34 6.9E-()6

370-180 1.01.6 120 168 9.58 7.0E-06

370-270 101.6 120 168 9.26 6.8E-06

avg= 7.0(.16)11-06

ff339 have very little variation. Willie Y307 NDR appears to

vary wilh x,y positlon. The NDR at 120 watts wýas

7.0(0.2JE-0-6 mid correspJonds to a 84% Increase in tei NIIR

at the higher powers.

Table C-2 shows the NDR bor a substrate height of 71nin11

W th-e chamber at 30 and 125 watts. For 30 watts the NDR

decreased wlih a I increase hi height to a valtuc of'

2.6(0.6)E-06. Tlhere was also a decrease hi NDR at 120

watts wlth the Increased height to a value of 4. i(t.4j1E-06.

Which is an increase' of 58% comlpared to 30 watts.

Table C-3 shows the NDR Ibr a heighl of 14rimi hi the

chamber at 30 mid 120 watts. The NDR decreased Fbr bothli

powers at tids height. At 30 watts tlie NDR decreased t.o

1.0(0.1)E-O(, wilde at 120 watts the NDR decreased to

2.7(0.2)E-06.

Figure C-I Is a graph of NDR vs deposition height. niid

power. For boUi powers, NDR decreases lIhearly as the,

chamber height Increases. The higher power clearly has a

12

"rIa 1)1e C-2

Normalized Deposition1 Rate for Z=7 nari

RUN It Diamet R( ThIe Mass N IW.

er (1 1) (watt (,Ii,) (ing) (ulg/1,1uA2

s) mill)

364-0 101.6 30 180 2.63 2.7E-(,)6

364-90 101.6 30 180 2.8 2.9--()6

364-1.80 1-01.6 30 180( 2.7 2.8 L.6

364-270 101.6 30 180 2.85 2.913-06

avg= 2.6(0.6)110)6

331-0 101.6 125 60 2.07 4.3E-06

331-90 10 1.6 1.25 60 2.33 4.81E-06

331-180 101.6 .125 60 2.29 4.711-06

331-270 101.6 125 60 2.44 5.0E-06

AVG.= 4.1(1.4) E-06

13

Table C-3

Normalized Deposition Rate for Z=14 .wn

RUN If Diameter Rf Time Mass NDM

(nun), (watts) (Ihitt) (1ng) (,,,g/1itil,, . ,,,iti)

376-0 101.6 30 180 1.53 1.0E-06

376-90 101.6 30 180 1.67 I.iE-06

376-180 101.6 30 1.80 1.46 1.01E-06

376-270 101.6 30 180 11.42 9.7.F7-07

AVG = 1.0(0.1) 1.-6

375-0 101.6 120 180 3.55 2.4E,-06

375-90 101.6 120 180 4.13 2.8E-06

375-180 101.6 120 180 4.11 2.8E -06

375-270 101.6 120 180 4.27 2.9-E-06

avg. =2.7(.2) Ei-06

'4i

fasterd~1 )O~tJ~t1 -alx,.11 dCIC)ellICII(C 01 )W a

height. does 1,0t. ljnii.4 tat, tMe somiie Comipositioni ;j~hw s

being deposited at Ilie v-rifous heights9. T1his "111i he

di1scussed In Ole next Sectiorn.

Figunre C-2 shows (1hC relatlonsiSlp betweeln NI)I? "iiid

power for diffeteut substvrates and higher poer nt.

chamiber height Mf7IXI. ti u~i ~iIiUSlt

reported above M11ti r esit ds obi ait ted fr'om qeiI c s

conducted wilhi Ms. Marilyn ii iec1lt.Lu 'Thiexci c k.

details of these runs xvvet di.scu-ssed hIn section LP. Thle open~

symbols i'neprscit. restil(s oI)AiltiId hIoni1 LICIMSIUMIS kon

represent metal, thus1 deposited Onl glass 7ii1n ubs1aes

Tile open Inverted an-d uprwight triangles are tlie results

for deposition Onl cithler glaIss slides or St wvCl~ers onl gkiss,

supports. For tlies e c0mnJplC tely IIIs lathig sb ae it

NDR clearlty Lucreases Itue,,irly wIMl I ncre.-sing power-.

Figur-e C- 1

Normallized Depositioni lt(te vs Power and I hegjht

¢0

2:

CII

S\ / KN

o6. ............... . .N

I

supports. At. 120 watts the NDR is nearly [lie same as 30

watts. But there is a steep Increase when the power is

Increased to 155 watts. At this power [lie deposition oil the

Si wafer Is greater than the corresponding depositions on

Insulating supports. And neai-ly as large aS the depositions

on the iiietal thiii I�Iiiis.

'Flie closed circles and squares are the results of

depositions on tutu lilnus If Al and Cu (respectively)

deposited on 7unuii glass substrates. At 120 watts there is

clearly a larger deposition rate for these substrates than the

Si containing materials. At 150 watts the change in NDR

Is not as large as the Si containing substrates. Which

suggest very hitUe dependence [or the substrates i.ipon l)�XVCV

levels above 120 watts.

2. AnalysIs of Deposition Composition

Each FF111 run couisisfed of l�ur wafers l)oslIloIle(l aroiiuid

the chamber at a fix.e(.1 cliauuiber height (Z). Fi'IR scauus (128

17

Appendix G

Experiments #4

Experhiment /14

Objective: To determine the effects of grounding the mietal substrateson the quality andI cliaracte'ristics of deposited carbon Ifilms(DLC)

Procedure: Substrates were n ietal-on -glass (2, Cu oii glass. 2, Al on glass).PrIor to cleaning qltuinilnumi foil leadis were -attached to thetabs of one Al plate and~ one Cul plate usIng small jpleccs of'Archer brand (64-0 10) tape solder (purch ased -,t RadioShack) and] -.pplying hecat to the top side of the roll with aiSol(lerIng iron. Plates were then riiised In (ap water mullvapor cleanedl in acetoneý vapor.

10

Substra~te Chamber Configuration:-

13- 11

pol t

P-10 p -82709 grounded Ic~900

grounded

Appendix H

Experiments H15 and #6

Experiment #5

Objective: To obtain thicker films than those previlously (ldeposited oilAl-on-g•ass plates and to imiake capacilor devi(es.. out of flhictifor evalntloti.

Procedure: Substrates were alulnlnI1rn-oil-glass (rellability plates). Pl•teswere cleaned by rinsing with tap water and dried In acetonevapors. Plates were weighed, heat tape (clut) were applied asmasked over the tabs (to prebase AM for later leadattachment), and plates were placed In the chamfnber asshown In the diagrain below.

4

Experiment #6

Objective: To ol)faiI .thilcker lliIls Man those prevlt)itsly deposItcd oil

al-on-glass i)l.tes anl to inale ca•lacitor (levices out otf I hemlot evaluation.

Procedure: 3 substrates were al-oil-giass (reliablIlly plates). I .1l,9ol"was Al 2 0 3 on Al-on-glass (relli•il.y plates) . All were were

cleane(d by riOsihg with tap wtefer 81m(d dried lin acelotivapors. IPlates were welghe(I, helal tape (ctii) imaslhed overtabis 8n1(1 p)lace(d Into a ctealt (1l11hl)er as •hown III the(lalgram• I)el•ow.

5

Appendix I

Planned Technical Accomplishments Section

of July 26, 1994 Quarterly Report

The next phase of this design Is the star or- composite

design. If there appears to be a lack of agrecinent between

the average responses of [lie center potint or non linearity,

four star points are taken together. These points along withl

the factors are eqluidistanti rromi thie center poinits. FIliese

new ruxis are thien randomized and time immiportamint cifbcts cand

hiteractions can be determilned by a linear regr-ession.

From this informat~on a response curve, which Is a

three-dhnentiona[, curve that pliots [lie response against the

factors, Is plotted. This curve should span some ranige and

thus Indicates [lie areas of niaxhnximix and minhiiniiimi

expernimenata parameters.

11. PLANNED TECHNICAL ACCOMPLISHMENTS

Thle following are p~lann~ed technical raccoIIpi)islinci its to be

conducted by the A&TI* segment of the A&TI - ]IATARDEC

research team that were generatted during tile July 11-13,

1994 Technical Meeting at A&'i':

(1) After tlie new flow mecters are Installed, (lie A&T segment of

the research team will redo Experiment /I 5 (see Appendix 2

for the objective and iprocedtire of Experiment II 5) imaking

any adjust-ments necessary to correlate [lie flow rates

*NOTE- Other parts of the Joint experiments will be cattiled out byr tcain mxcniiilxs at IATand ARDEC

12

(2) The A&T segmuenit of lhe researcli team will correklatereadings of the old flow controllers oi the del)osition system

and the newly-ordered flow meters.

DLC flhns needed In Experiment #f 6 (see statement of

Experhient # 6 and Its purpose In Appendix 2). The

substrates will be 12 glass plates on which aluminhum 1%

copper (AI/l% Cu) filns have been deposited by a

standardized physical vapor deposition process utilizing

resistance heathig. The nmetal fihi layer will be nominally 2

microns thick and shall be examinied prIor to I)LC depositioln

to enisure superior adheslom of tihe Al/l% Cu to the glass

(samples tested sh ould exhibit adi 1eslo01s greater I11 mal10,000 psi as meastlred by the Sebasilli ill adhlerillcc

tester.)

All of the substrates will be coated wlthI a I)LC ullm rslhig (ihePECVD technique at A&T. The deposition t)arrameters are to

be Identical except for the time of rui, 1. e. thickness of thedeposits will be the experinental variable. Since tle

deposition system at A&T can only accept four of the

substrates In one run (due to the physical size of lhe

deposition chaniber), three runs will be required to coat the

12 substrates; therelbre, three different DLC thicknesses will

be produced.

(3) The A&T segment of the researclh teamn will make the DLC

flinis needed lit Exxperiment # 7 (see statemnent of Experiment

13

, J

1#7 and its purpose In Appendix 2). Thi substrates will be 12

glass plates supplied by ARDEC on which alumhlnun 1%

copper (AI/I%C.u) ilmns are deposited by a standardized

physical vapor deposition process uttilizing resistance

heating. The imetal Himih layer will be iomiltinlly 2 itil(r(tis

thick and shall be exmilned prior to DI.C deposiloll to

ensure superior adhesion of the All %Cu to the glass

(samples tested should exhibit adhesions greater than

10,000 psi as measured by (he Sebastlan III adherence

tester.) Nine of these plates will be anodized under a

standardized process so that ma AI2 0 3 layer of nominal

thickness of about 0.3 microns Is formed.

All 12 of the substrates will be coated with a DLC llm ushig

the PECVD technique at A&T In which the deposition

parameters are Identical except for the time of the rmtil, 1. e.thickness of the deposits will be the experhiental varl.able.

Since the deposition system utilized at A&T can only acceptfour of the substrates In one run (due to the physical size of

the deposition chamber), three runs will be required to coat

the 12 substrates; one Al-on-glass plate with three

AI/A120 3 -on-glass plates will comprise each run. "h'llree

different DLC thicknesses will be produced.

141

APPENDICES

V APPENDJIX 1

MASS FLOVMETER

CONVERSION FACTORS

GAS SYMBOL CALIBRATION DIAL SEI-ING

Coll" 6

Aceylene .1.00

Air Nil' 68

Argon A 1.44

Arsgno A51C) .66

Boron Ttichloride . FI .61

Boron Trifluoridw fOr

.61

Carbon Dioxide COI

.74

Carbon Monoxide CO

1.00

Chlorin0e Cl1'

.84

Diborane 01!!'

.44

Dichlorositan'll

.44

Dichloro Mbethyl Silane (CI I') 2 SiC1' .23

Ethane C111'

.A9

Ethylene CCI,14

.60

Freon-12 CCFU

.32

Freon-14 CP

.42

S Fr eon-2 2 C( ICIFI .4.

Germane G4iP

.60

l~e 1.,43

Helium" le

1.0

Hydrogen I

1.02

tlydrogen Bromide I l~

1.04

Hydrogen Chloride I IC.9

Hydrogen Fluoride IIF

.001

I-lydrogen Seienide Illse

.81

Hydrogen Sulfide IIS .'9

Krypton

1.49

Metlhane Clio

.72

Methanol CIPO1l

.58

Me'thyl Trichlorosilatri (CtH') SiCl

.25

Nitric Oxide NO

.99

Nitrogen NO .00

Nitrogen Dioxide N'O

.73

Nitrous Oxide O0 '.73

Oxygen 1.00

Phosphine Pi'

.69

Propane C it' .43

Propylene sill' .59

Sila ti SiCll .29

Silicon Tetrachloride So, .66

Sulfur Dioxide SF .28

Sulfur Ilexafluoride SEA .22

Tungsten Hlexafluoride X' .22

X en o n Xe

1.36

"--ri c1 n r l atie Si ICI .35

Trichloosilan

Appendix 2: Somue Details or ExIpenrillcIt~s 115, 116 fad 117.

E xperiment #5

Objective: To obtain thicker filinus Hu ta Ihose previollsly dlepositedf oilAl-oil-glass plates 811( to mtake copnelit.or devices oul of, t hemlfor evaluation.

Procedure: Substrates Were alumutilIMIuII-oti-glass (reClinbillty plates). Plateswere cleanied by rlinsinig withI tap water and( drtiedl tii cc onlevapors. Maltes were weighedI. hetIape (cuti) Were aJ)Jpliedl nsmiasked over tile tabs5 (to) jprCI8se At fiw laici- led

Exioerlinent #/ODescription:

Determnliatilon of(lie ieffec of, thickiness, ol dielectlric ,3tl.(.ilgt 1(breakdown voltage) For l)LC Mlls p~rodulced býy I'ECWJ.

Purpose: To determine how breakdown voltage of parallel plate c8J~adi-toys fabricated with lP1.CVD DLC M~is varies wvithi dielectric.thickness.

Experiment # 7Description:

Determiniationi of tile effect. of a, layeredl composite dilelectricand( layer tilicklless of (lielectrie st reingth (breakdown voltage).and~ DC leakage current for i)JiC films prodlucedl by l~C it,a layered A12 03 /DLC ohlelectnic systeim.

Purpose: I) To determline tile cillect. of ', layered compJosite dielect lie Sys-temi colllirishiig a thiiii f~lhi of A12 013 unider a DIXC 11111 oil tile

D)C leakaluge en rr-ciit and( ibieaklow;il Voltage of paranllel pla eC~rlpacitors.

2) To oleterniiiiie how I)tCr((lO~lk1oI volt age of' Jmaralicl 1)181 e (almci-tors fabricated withI layered compllosit~e dlielectric comlprised of*a thin Minu of AL2 03 milder PE'ICVi) DLC thini filills varileswith DLC tliickiies.

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