A STUDY OF THE INTRODUCTION OF IONS INTO THE REGION O F STRONG F I E L D S W I T H I N A QUADRUPOLE MASS SPECTROMETER

Wilson M. Brubaker

ABSTRACT

Experiments w ith t h e round and t h e hype r bolic quadrupole u n i t s have been continued, The preliminary d a t a which were obtained pr e v i o u s l y have been s u b s t a n t i a t e d . The r e s o l v i n g power of t h e hyperb o l i c quadrupole 1s about twice t h a t of t h e round a t comparable sensltivitieg, Resolving power of 600, measured a t t h e 1 % 0 peak height, w a s obtained w i t h t h e hyperbolic u n i t a t a transmission e f f i c i e n c y of 20%, when excited a t v e r y low power, A t highe r power, a r es o lv in g power of 1000 was obtained a t 10% tr a nsmission e f f i c i e n c y , Flat-topped peaks were observed a t r e s o l v i n g powers below 400.

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TABLE OF CONTENTS Page

LISTOFFIGURES INTRODUCTION
o o
a

, .

, .

,.

*..
o

.
0

iii
o

APPARATUS AND EXPERIMENTAL PROCEDURE

QUADRUPOLE PERFORMANCE DATA

rn

4
6

CONCLUSIONS

NEXTQUARTER'S ACTIVITIES FIGURES 1 APPENDIX

16

. ,

.... .

, ,

-6

"The Efficient Introduction of Ions into a Quadrupole Mass Filter," presented at the Fifteenth Annual Conference on Mass Spectrometry and Allied Topics, Denver, May 14-19, 1967, ,

1 . "The Efficient Introduction of Ions into a Quadrupole Mass 1 Spectrometer," accepted for inclusion in Proceedings of Fifteenth Annual Conference on Mass Spectrometry and Allied Topics, Denver, May 14-19, 1967,

111, "Improved Quadrupole," accepted for presentation at the Mass Spectroscopy Conference in Berlin, September 25-29, 1967, and for publication in "Advances in Mass Spectrometry," Volume 4 .

-iii-

LIST OF FIGURES

Figures

1 .
2,

Sensitivities of Ion Sources as a Function of Ion Energy, Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of Resolving Power. Excitation Frequency 0,707 MHz, Ion Energy 1 volt. Normalized Sensitivities of Round and Hyperbolic Quadrup o h e as Functions of Resolving Puwer, Excitation Frequency 1-0 MHzJ Ion Energy 2 volts. Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of ~esolvingPawerr Excitation Frsquency 1 4 4 M H z , Ion Energy 4 volts4 ,1 Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of Resolving Power. Excitation .0 Frequency 0 7 7 M H z , and 1,414 M H z . Ion Energy 1 volt, Multiple Scans of Mass 84 Peak at Various Resolving Powers, . Excitation Frequency 1,414 MHzj Ion Energy 10 V o l t ,

3,

4,

54

6.

INTRODUCTION

T h is r e p o r t covers t h e work done by t h e B e l l & H o w e l l Research Center on NASA Contract NASW-1298 from 1 7 February through 17 May, 1967. Thi s is t h e seventh q u a r t e r of t h e Contract. This p r o j e c t i s concerned with t h e intr oduc tion of ions i n t o t h e r egion of stro n g f i e l d s i n t h e quadrupole mass f i l t e r , and w ith t h e comparison of t h e performances of quadrupole s t r u c t u r e s w ith round and with hyperbolic field-forming sur f a c e s , During this q u a r t e r a d d i t i o n a l d a t a have been obtained which compare t h e operatio n of t h e two quadrupoles. The supe r ior performance of t h e hyperbolic r o d s is now w e l l e sta blishe d.

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APPARATUS AND EXPERIMENTAL PROCEDURE

The apparatus is th e same a s t h a t described i n l a s t q u a r t e r ' s r e p o r t , with th e exception t h a t an electrometer a m p l i f i e r and a X-Y recorder have been used a s read-out devices i n place of the o s c i l l o g r a p h , The only change i n t h e experimental procedure i s t h a t a ssoc ia te d with the change i n t h e read-out devices used,

As before, th e krypton spectrum w a s used f o r t h e s e t e s t s , The s e n s i t i v i t y as a f u n c t i o n of resolving power i s a ga in used t o d i s p l a y t h e performance of t h e instruments.

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EXPERIMENTS

The prime o b j e c t i v e during t h i s q u a r t e r was t h e comparison of t h e o p e r a t i o n of t h e two quadrupoles, one with round and t h e othe r w i t h hyperb o lic su rfaces. Data were obtained which i n d i c a t e t h e s e comparisons when the quadrupoles were operated i n t h e delayed dc ramp mode,

Two s e t s of experiments were performed. In one, the number of c y c l e s of r a d i o frequency which occur during t h e i o n t r a n s i t was held constan t w h ile t h e e x c i t a t i o n frequency was v a r i e d over a f a c t o r of two. The i o n energy varied by a f a c t o r of four, and t h e power required t o e x c i t e t h e system v a r i e d about 30 times! In t h e o t h e r set of experiments, t h e ion energy remained low while t h e e x c i t a t i o n frequency was again varied over t h e two-to-one range. Under the se c onditions e xc e ptiona l r e s o l v i n g power a t high transmission e f f i c i e n c y was obtained with t h e hyperb o lic quadrupole.

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QUADRUPOLE PERFORMANCE DATA

In t h e f i r s t s e t of experiments the number of radiofrequency c yc le s which occur while th e ions t r a v e r s e the f i l t e r is 110. For t h e round rod quadrupole, t h i s should give a r e solving power of 475, according t o the semi-empirical formula given by Paul. The e x c i t a t i o n frequencies were 0.707, l o o , and 1.414 MHz, and the corresponding ion i n j e c t i o n e ne r gie s were 1, 2, and 4 v o l t s . Data comparing t h e performance of t h e round and t h e hype r bolic u n i t s a r e presented i n F ig u res 2, 3, and 4 . I n each case the s e n s i t i v i t y of t h e hyperb o lic u n i t was a r b i t r a r i l y s e t a t loo%* The response of the round u n i t , op eratin g under t h e same conditions, is given i n i t s r e l a t i o n t o t h a t of t h e hyperbolic, The s e n s i t i v i t y of the round u n i t i s c o n s i s t e n t l y lower than t h a t of t h e hyperbolic, even a t u n i t r e solving power. This d i f f e r e n c e is not found i n the sour c e se I n t e r e s t i n g l y (and u n a n t i c i p a t e d l y ) the d i f f e r e n c e a t t h e lowest r e solving power i n c r e a s e s with e x c i t a t i o n frequency, I n t h e comparison of t h e da ta i n t h e t h r e e f i g u r e s , t h e v a r i a t i o n i n t h e output of t h e ion source a s a f unc tion of ion energy a s displayed i n Figur e 1 should be kept i n mind, The d a t a a s presented here a r e normalized t o t h e s e n s i t i v i t y of t h e hyperbolic u n i t , and do not i n d i c a t e t h e r e l a t i v e s e n s i t i v i t i e s of t h e instruments when operated a t t h e d i f f e r e n t f r e quen c i e s , This manner of p resen tin g t h e data i s chosen t o emphasize t h e d i f f e r e n c e s i n t h e performances of t h e round and t h e hyperbolic quadrupoles when they a r e operated i n i d e n t i c a l mannerso I f a l l of t h e p o t e n t i a l s i n the u n i t s were sc a le d i n proportion, t h e d a t a of t h e t h r e e f i g u r e s should a l l be a l i k e , That they a r e d i f f e r e n t i n d i c a t e s t h a t some of t h e p o t e n t i a l s d i d not v a r y i n t h e same pr opor t i o n , I n t h e o p eratio n of t h e instruments t h e sources were a djuste d f o r maximum output of unresolved io n c u r r e n t a t each l e v e l of ion energyo Unfortun a t e l y , t h i s d i d not occur a t pr opor tiona l v o l t a g e s on t h e ion focus e l e c t r o d e i n t h e ion source. However, i t is most probable t h a t t h e r e were o t h e r and more important p o t e n t i a l s which d i d not v a r y i n pr opor t i o n , In p a r t i c u l a r , t h e r e a r e t h e p o t e n t i a l s i n t h e ion source which r e s u l t from t h e space charge of t h e e l e c t r o n beam, I n a d d i t i o n , t h e r e may have been i n s u l a t i n g s u r f a c e s which r e s u l t e d from e xte nsive ion bombardment. The d a t a of Figure 2 a r e of p a r t i c u l a r i n t e r e s t . Here t h e e x c i t a t i o n frequency was only 0,707 MHz, and t h e maximum a c p o t e n t i a l on t h e rods was only 130 v o l t s a t mass 86: Even so, t h e performance of t h e hype r b o l i c rods i s v e r y impressive. A r e solving power of 500 i s obtained a t a s e n s i t i v i t y which is 44% of t h a t observed a t low r e s o l v i n g power,

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The most s i g n i f i c a n t f a c t o r i n t h e comparison of t h e two quadrupoles is t h e reso lv in g power observed a t constant s e n s i t i v i t y . On t h i s b a s i s , t h e hyperbolic quadrupole outperforms the round by a f a c t o r of two! When i t i s r e c a l l e d t h a t th e only known d i f f e r e n c e between the two u n i t s is t h e shape of t h e rods the confidence i n the d a t a i s e x c e l l e n t . Fur t h e r , a s mentioned i n t h e l a s t r e p o r t , the d a t a were not a l t e r e d when t h e rods were interchanged i n t h e two vacuum envelopes. The sources and d e t e c t o r s remained w i t h t h e i r o r i g i n a l envelopes.

I n t h e second set of experiments, t h e ion energy was he ld a t one v o l t and t h e e x c i t a t i o n frequency va r ie d. As expected, t h e r e solving power increased as t h e frequencywas r a i s e d . These d a t a a r e presented i n Figure !5* The n o rmalization i s t o t h e hype r bolic s e n s i t i v i t y a t each of t h e two e x c i t a t i o n frequencies. Again, t h e r e s o l v i n g power of t h e
hyperb o lic exceeds t h a t of t h e round by a f a c t o r of two f o r comparable s e n s i t i v i t i e s , Flat-topped peaks a r e obtained with t h e hyperbolic t o a r e s o l v i n g puwer of about 400. A t a r e s o l v i n g power of 1000 t h e t r a n s mission e f f i c i e n c y i s dawn only t o lo"/,. Figure 6 shows a s e r i e s of scans aver t h e mass 84 peak a s the r e s o l v i n g power w a s v a r i e d . Most quadrupole peaks a r e asymmetrical. In t h e conventional mode of ope r a t i o n , t h e high mass s i d e of t h e peaks have t h e s t e e p e r slope . That t h i s should be so is seen by r e f e r r i n g t o t h e s t a b i l i t y diagram and noting t h a t t h e scan l i n e c r o s s e s t h e y - s t a b i l i t y l i m i t obliquely, and t h e x - s t a b i l i t y In t h e delayed d c ramp mode of operation, the l i m i t n e a r l y normally. s l o p e is s t e e p e r on t h e low mass s i d e of t h e peak. This change must be due t o t h e avoidance of th e y-unstable c ondition a t t h e e ntr a nc e t o t h e quadrupole.

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CONCLUSIONS

The experimental work done during t h i s q u a r t e r h a s compared the performance of t h e round and t h e hyperbolic quadrupoles. I n every instance t h e r e s o l v i n g power of t h e hype r bolic ha s been found t o exceed t h a t of t h e round by about a f a c t o r of two, f o r s i m i l a r s e n s i t i v i t i e s . With t h e hyperbolic quadrupole, operated i n t h e delayed dc ramp mode, a r e s o l v i n g power of 1000 a t the 1077 p o i n t ha s been obtained with a transmission e f f i c i e n c y of 10"L.

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NEXT QUARTER'S ACTIVITIES

During the next quarter the data w i l l be refined and the s e n s i t i v i t i e s w i l l be placed on an absolute scale. Theoretical and experimental work will be done on the ion source, with a goal of obtaining higher s e n s i t i v i t y a t the lower ion energies.

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Sensitivities of Ion Sources as a Function of Ion Energy

3 4 Ion Energy, Volts

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..... . . ...... . . . .--. .. .-. _ . . . ,. . . .

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! I

- e - l
;

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I :

Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of lesolving Power. Excitation Frequency 0.707 MHz, I o n Energy 1 volt.

100

200

300

400

500

600

700

Resolving Power at 10% of Peak Height

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Figure 3 Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of Resolving Power. Excitation Frequency 1.0 MHz, Ion Energy 2 volts.

100

200

300

400

500

600

700

Resolving Power at 10% of Peak Height

Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of Resolving Power. Excitation Frequency 1.414 MHz, Ion Energy 4 volts.

100

200

300

400

5 00

600

700

Resolving Power at 10% of Peak Height

Figure 5 Normalized Sensitivities of Round and Hyperbolic Quadrupoles as Functions of Resolving Power. Excitation Frequency 0.707 MHz, and 1.414 MHz. Ion Energy

150

300 45 0 600 750 RESOLVING POWER A T 10% OF PEAK HEIGHT

1,050

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A- 1

APPENDIX

A paper, entitled "The Efficient Introduction of Ions Into a Quadrupole Mass Filter" was presented at the Fifteenth Annual Conference on Mass Spectrometry and Allied Topics in Denver, May 14-19, 1967.

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I1

Manuscript accepted f o r inclusion i n Proceedings of F i f t e e n t h Annual Conference on Mass Spectrometry and A llie d Topics, Denver, May 14-19, 1967
THE EFFICIENT INTRODUCTION OF IONS INT.0 A Q A R P L MASS SPECTROMETER* U D UO E

Wilson M e Brubaker B e l l & Howell Research Center Pasadena, C a l i f o r n i a

ABSTRACT

The e f f i c i e n c y w i t h which ions a r e introduced i n t o a quadrupole mass f i l t e r i s increased by s e v e r a l powers of t e n by t h e a ppr opr ia te c o n t r o l of t h e f i e l d s a t t h e entrance t o t h e f i l t e r . This i s accomplished by using an a d d i t i o n a l set of fo u r el e c tr ode s, The p o t e n t i a l s applied t o t h e s e a d d i t i o n a l e l e c t r o d e s have a smaller r a t i o of dc t o a c va lue s than t h e p o t e n t i a l s applied t o t h e quadrupole, Computer s t u d i e s r e v e a l t h e high v u l n e r a b i l i t y of t h e e n t e r i n g ions t o t h e impulses which they r e c e ive a s they traverse t h e f r i n g e f i e l d s of t h e conventional quadrupole. Fur the r s t u d i e s w ith t h e computer reveal the e f f e c t i v e n e s s of t h e a l t e r e d f i e l d s i n elim in atin g th ese undesired impulses, Experimental d a t a compare t h e oper at io n of t h e quadrupole with and without use of t h e a d d i t i o n a l e l e c t r o d e s , It i s found t h a t t h e s e n s i t i v i t y of t h e instrument can be increased by powers of t e n without degrading t h e r e solving power through t h e use of these auxiliary electrodes,

***********
It has long been recognized t h a t t h e r e i s a d i r e c t r e l a t i o n s h i p between t h e reso lv in g power of the quadrupole and t h e number of c yc le s spent by t h e ions i n t r a v e r s i n g the device, Increasing t h e frequency of e x c i t a t i o n and decreasing t h e a x i a l v e l o c i t y both inc r e a se t h e t r a n s i t t i m e i n periods of t h e a c e x c i t a t i o n , The former i s accomplished only a t a g r e a t expense i n power, and t h e l a t t e r w ith a decrease i n s e n s i t i v i t y , The severe a t t e n u a t i o n of t h e transmission of i o n s through t h e quadrupole which r e s u l t s from d i r e c t i n g ions toward t h e instrument a t low v e l o c i t y occurs because t h e ions r e c e i v e a l a r g e component of r a d i a l v e l o c i t y a s they t r a v e r s e t h e f r i n g i n g f i e l d s .

* This

research w a s supported i n whole o r i n p a r t by t h e National Aeronautics and Space Administration under Contract N o , NASW-1298, monitored by D r , Donald P. E a s t e r ,

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Through an a l t e r a t i o n of the r e l a t i v e s t r e n g t h s of t h e dc and t h e a c f i e l d s a t t h e entrance t o t h e quadrupole i t is p o s s i b l e t o avoid t h e severe loss of low v e l o c i t y ions, This a l t e r a t i o n of t h e f i e l d s is accomplished through t h e use of an a d d i t i o n a l set of four e l e c t r o d e s i n t h e v i c i n i t y of t h e entrance a p e r t u r e , I This refinement i n the quadrupole s i g n i f i c a n t l y decreases the s i z e of t h e instrument and t h e requir ed power f o r a given r e solving power. These c onside r a tions a r e p a r t i c u l a r l y important fDr space a p p l i c a t i o n s ,

me u su al use of the s t a b i l i t y diagram i s t o i n d i c a t e t h e manner i n which t h e mass spectrum is produced, In t h i s disc ussion it is used t o h e l p understand what happens t o an ion as i t pa sse s through t h e f r l n g e f i e l d s while e n t e r i n g t h e quadrupole, A s an ion e n t e r s the quadrupole on a path which i s p a r a l l e l t o t h e instrument a x i s , t h e v a l u e s of both a and q v a r y from zero t o f u l l v a l u e , For ions which a r e tran smitted through t h e quadrupole a t high r e s o l v i n g power t h e l o c u s of th e working p o i n t l i e s very c l o s e t o t h e apex of t h e s t a b i l i t y diagram while t h e ion i s w i t h i n the quadrupole. During almost a l l of t h e t r a n s i t of t h e ion through t h e f r i n g e f i e l d s , t h e working p o i n t l i e s f a r above t h e y - s t a b i l i t y l i m i t , Here the a c c e l e r a t i o n i s d i r e c t e d away from t h e instrument axis.
I f th e path of t h e working point a s t h e ion e n t e r s the quadrupole can be made t o l i e w i t h i n the s t a b l e p o r t i o n of the s t a b i l i t y diagram, t h e undesired y-directed impulse can be avoided. This d e s i r e d situa st i o n can 'be achieved i f t h e working point mmes f i r s t a l m g t h e q- a xi s as i t leav es t h e o r i g i n . Such motion is obtained i f t h e field-forming s u r f a c e s ad jacen t t h e entrance a pe r tur e a r e e x c i t e d w i t h a c p o t e n t i a l s only, These a d d i t i o n a l e l e c t r o d e s f i e between t h e e ntr a nc e a p e r t u r e and th e u s u a l quadrupole rods whish a r e e xc ite d w ith t h e i r normal amounts of a c and dc p g t e n t i a l s * Because the d c f i e l d s a r e delayed (along t h e instrument a x i s ) g t h i s mode of ope r a tion has been termed "delayed d c ramp". Experiments were made i n which e i g h t - v o l t ions were i n j e c t e d i n f o a ten-inch quadrupole o p erating a t 1,6 MHza D i r e c t c3mparison of t h e operatio n i n t h e conventional and the delayed dc ramp modes were made. A t t h e modest r e s o l v i n g power of 100 t h e s e n s i t i v i t y of t h e delayed dc ramp mode was 50 times t h a t of the c onve ntiona lo A t a r e s o l v i n g power of 400 t h i s d i f f e r e n c e becomes 250. I n t h e conventiona.1 quadrupole, a s ha s j u s t been shown, the use of

low i n j e c t i o n energy i n c r e a s e s t h e number of c y c l e s spent by t h e ions

i n t r a v e r s i n g t h e f r i n g e f i e l d s and causes se ve r e a t t e n u a t i o n of t h e transmission e f f i c i e n c y . Conversely, i f high tr a nsmission e f f i c i e n c y is obtained by using h ig h er i o n i n j e c t i o n e ne r gie s, then t h e upper l i m i t of t h e r e s o l v i n g power i s reduced,

A-4

I n th e improved quadrupole, operating i n t h e delayed dc ramp mode, ions can be introduced a t low energies without causing the transmission e f f i c i e n c y t o be low. Thus high r e solving puwer a t high s e n s i t i v i t y can be achieved.

REFERENCES

'. M. Brubaker, "Auxiliary Electrodes of Quadrupole Mass F i l t e r a , " W U. S, P aten t 3,129,327,

A more d e t a i l e d paper w i l l be published i n "Advances i n Mass Spectrometry," Volume 4 , (Proceedings of I n t e r n a t i o n a l Mass Spectrometry Conference, Berlin, September, 1967).

A-5
I11

Manuscript accepted f o r p rese nta tion a t the Mass Spectroscopy Conference i n Berlin, September 25-29, 1967, and f o r p u b l i c a t i o n i n "Advances i n Mass Spectrometry," Volume 4 , I P O E QUADRUPOLE* MR V D Wilson M, Brubaker

B e l l & H o w e l l Research Center Pasadena, Ca lif or nia

ABSTRACT

Experimental d a t a r e v e a l t h a t the s e n s i t i v i t y of the conventional quadrupole can be increased by a f a c t o r of t e n t o one-hundred with no s a c r i f i c e i n th e reso lv in g power. This is accomplished through the use of a set of four a d d i t i o n a l e le c tr ode s a t the ion entrance end of the mass f i l t e r . As an ion tr a ve r se s the f r i n g e f i e l d s of a convent i o n a l quadrupole th e working point moves through t h e y-unstable port i o n of the s t a b i l i t y diagram. Under these circumstances, computer s t u d i e s have shown t h a t t h e ion receives a la r ge impulse i n the yd i r e c t i o n . By ap p ro p riately energizing the a u x i l i a r y e l e c t r o d e s of t h e improved quadrupole, it is possible t o have the working point remain w i t h i n t h e x- and y-stable portion, and thus t o avoid t h e undesirable r a d i a l impulse. The r e s u l t s of computer s t u d i e s and experimental d ata are presented,
INTRODUCTION

The quadrupole mass f i l t e r i s uniquely d i f f e r e n t from most other m a s s analyzers. Its maximum dimension i s along t h e a x i s , y e t the f i e l d s w ith in th e s t r u c t u r e have no component i n t h i s d i r e c t i o n . Additional length of the instrument se r ve s merely the purpose of increasin g th e time spent by the ions i n t r a v e r s i n g t h e analyzer. It has long been recognized' t h a t the r e is a d i r e c t r e l a t i o n s h i p between the reso lv in g power of the quadrupole and the number of c yc le s Increasing t h e frequency spent by t h e ions i n t r a v e r s i n g the device. of e x c i t a t i o n and decreasing t h e a x i a l v e l o c i t y both inc r e a se the t r a n s i t t i m e measured i n p er iods of the ac e x c i t a t i o n . The former is accomplished only a t a g r e a t expense i n dr iving power, and the l a t t e r r e s u l t s i n a decrease i n s e n s i t i v i t y , The severe a t t e n u a t i o n of t h e transmission of ions through the quadrupole which r e s u l t s from

* This

research w a s supported i n whole or i n p a r t by t h e National Aeronautics and Space Administration under Contract No. NASW-1298, monitored by D r , Donald P. Easter.

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d i r e c t i n g ions i n t o t h e instrument a t low v e l o c i t y occurs because t h e i o n s receiv e a l a r g e component of r a d i a l v e l o c i t y a s they t r a v e r s e the fringing f i e l d s . Through an a l t e r a t i o n of the r e l a t i v e s t r e n g t h s of t h e dc and t h e a c f i e l d s a t t h e en tran ce t o t h e quadrupole i t i s p o s s i b l e t o avoid t h e severe 108s of low v e l o c i t y ionsea This a l t e r a t i o n of the f i e l d s is accomplished through t h e use of an a d d i t i o n a l s e t of f o u r e l e c t r o d e s i n t h e v i c i n i t y of t h e entrance a p e r t u r e o This refinement i n t h e quadr u p o l e s i g n i f i c a n t l y decreases t h e size of t h e instrument and t h e requi red d r i v i n g power f o r a given r e s o l u t i o n . These c o n s i d e r a t i o n s are p a r t i c u l a r l y important f o r space a p p l i c a t i o n s ,

THEORY

General d i s c u s s i o n of t h e theory of t h e quadrupole mass f i l t e r requires referen ce t o t h e s t a b i l i t y diagram, shown i n Figur e I, The coor d in ates a r e t h e dimensionless numbers a and q. For a given r a t i o of t h e d c t o t h e a c p o t e n t i a l s , the %orking point" f o r ions of a l l v a l u e s of m / e f a l l on a s t r a i g h t l i n e which pa sse s through t h e o r i g i n , This is denoted a s th e "scan line". The u s u a l u se of t h e s t a b i l i t y diagram is t o i n d i c a t e the manner i n which t h e mass spectrum is produced. I n t h i s d i s c u s s i o n i t is used t o he lp understand what happens t o an i o n a s i t passes through t h e f r i n g e f i e l d s w h ile e n t e r i n g the quadrupole, F i r s t , i t should be noted t h a t th e dimensionless v a r i a b l e s a and q a r e p r o p o r t i o n a l t o t h e f i e l d s a t a given p o s i t i o n i n the plane t r a n s v e r s e t o t h e instrument a x i s . Thus, a s an ion e n t e r s th e quadrupole on a path which i s p a r a l l e l t o t h e instrument a x i s , t h e v a l u e s of both a and q va r y from zero t o f u l l v a l u e . For io n s which a r e transmitted through t h e quadrupole a t high r e s o l v i n g power t h e focus of the working point must l i e very c l o s e t o t h e apex of t h e s t a b i l i t y diagram w hile t h e i o n is w i t h i n t h e quadrupole. Theory p rev io u sly developed3 shows t h a t t h e r a d i a l a c c e l e r a t i o n experienced by an ion a s i t responds t o t h e combined dc and ac f i e l d s is p r o p o r t i o n a l t o t h e v e r t i c a l d i s t a n c e between t h e y - s t a b i l i t y l i m i t and th e working p o i n t . The working p o i n t i n t h e quadrupole f o r a tr ansm itted ion l i e s very ne a r t o t h e apex, j u s t under t h e y - s t a b i l i t y limit, and t h e n e t a c c e l e r a t i o n i s d i r e c t e d toward t h e instrument a x i s . But during almost a l l of t h e t r a n s i t of t h e ion through t h e f r i n g e f i e l d s , t h e working p o i n t l i e s f a r above t h e y - s t a ' b i l i t y l i m i t , Here t h e a c c e l e r a t i o n is d i r e c t e d away from t h e instrument a x i s . Computations have shown t h a t t h e magnitude of t h e y-directed momentum impulse which t h e i o n r e c e i v e s a s it t r a v e r s e s t h e f r i n g e f i e l d s v a r i e s e x p o n e n t i a l l y w i t h t h e number of p erio d s ( c yc le s) of ac e x c i t a t i o n which occur during

A- 7

i t s t r a n s i t . Thus i t is seen t h a t t h e number of c y c l e s spent by t h e i o n s i n t h e f r i n g e f i e l d s m u s t be kept q u i t e small, unle ss t h e r e i s t o be an acute a t t e n u a t i o n of the transmission of ions through the instrument. I f t h e path of t h e working point can be made t o l i e w i t h i n t h e s t a b l e p o r t i o n of t h e s t a b i l i t y diagram while t h e ions a r e passing through t h e f r i n g i n g f i e l d s , t h e undesired y- dir e c te d impulse can be avoided. This d e s i r e d s i t u a t i o n can be achieved i f t h e working point m o v e s f i r s t along the q-axis as i t le a ve s t h e o r i g i n . Such motion is obtained i f the ficld-forming sur f a c e s a dja c e nt t h e e ntr a nc e a p e r t u r e are excited w i t h ac p o t e n t i a l s only. These a d d i t i o n a l e l e c t r o d e s l i e between t h e en tran ce a p e r t u r e and t h e u s u a l quadrupole r ods which are excited w i t h t h e i r normal amounts of a c and d c p o t e n t i a l s , Because t h e d c f i e l d s are delayed (along t h e instrument axis), t h i s mode of o p e r a t i o n h as been t e r m e d "delayed d c ramp", One of t h e many p a t h s t h e working p o in t may tak e through t h e s t a b i l i t y diagram i n t h e delayed d c ramp mode of o p eratio n i s denoted a s a "preferred path" i n Figure 1.

COMPUTER STUDIES

The purpose of t h e computations was t o e v a l u a t e the s e r i o u s n e s s of pe rmittin g t h e working p o i n t t o m o v e through t h e y-unstable p o r t i o n of t h e diagram a s t h e ions t r a v e r s e t h e f r i n g e f i e l d s of the convent i o n a l quadrupole, Computations were made i n which t h e ions were assumed t o be formed w i t h i n t h e quadrupole, t o e n t e r a conventional quadrupole with co in cid en t (normalized) dc and a c ramps, and t o e n t e r t h e improved quadrupole, i n t h e delayed d c ramp modeo
Computer s t u d i e s d i f f e r from l a b o r a t o r y s t u d i e s i n t h a t the t r a j e c t o r y is never terminated by the ions s t r i k i n g t h e rods. The amplitude is l i m i t e d only by t h e number of d i g i t s i n t h e computer, This was never a concern during th ese i n v e s t i g a t i o n s The a, q v a l u e s chosen f o r t h e t o a r e s o l v i n g power of about 400. l i e s v ery c l o s e t o t h e l i n e px Sy x and t h e y t r a j e c t o r i e s a r e ne a r ly uniform f i e l d r e gion correspond Fur the r , t h e working p o i n t s e l e c t e d = I, s i n c e t h e envelopes f o r t h e i d e n t i c a l f o r t h i s va lue .

I n t h e f i r s t s e t of c a l c u l a t i o n s t h e i o n s were assumed t o be formed w i t h i n t h e uniform f i e l d region, with z e r o r a d i a l v e l o c i t y , and a t t h e p o i n t x = y = I, Since t h e x and t h e y f o r c e s a r e comp l e t e l y orthogonal and independent of each othe r , t r a j e c t o r i e s f o r both components of motion were obtained simultaneously, T r a j e c t o r i e s were s t a r t e d a t 90 phase i n t e r v a l s (of t h e a pplie d a c p o t e n t i a l ) .

A-8

The maximum amplitudes were i n general s i m i l a r f o r x and y motions, The amplitudes remained t h e l a r g e s t a t 90 and 270, a s expected. l e s s than 25 times the i n i t i a l displacement. In t h e second s e t of computations the passage of the ions from regio n s of zero f i e l d s t o those of f u l l f i e l d s was simulated by causing th e magnitudes of the f i e l d s (dc and a c ) t o inc r e a se together a t a uniform r a t e from zero t o t h e i r f u l l values. Computations were again made a t the four phase angles, and f o r ramp le ngths of two and ten cycles. In a l l cases the maximum amplitude f o r t h e x-component of motion is less than t e n t i m e s the i n i t i a l position, but f o r the y-component a t ten-cycle ramp the normalized amplitudes a r e a l l g r e a t e r h than 1000 times the i n i t i a l displacement! T e phase of the ac p o t e n t i a l a t th e start of t h e computations has l i t t l e influence on these extremely l a r g e amplitudes, Further computations were made i n which t h e independent v a r i a b l e is the number of cy cles which occur while the ions t r a v e r s e f r i n g e f i e l d s . As might have been a n t i c i p a t e d , the maximum amplitude v a r i e s expo n en tially with the ramp length, measured i n c yc le s (periods) of ac e x c i t a t i o n . In th e t h i r d s e t of computations the ions were assumed t o e n t e r t h e quadrupole i n th e delayed d c ramp mode. Several d i f f e r e n t "preferred paths" were used. In t h e s t e e p e s t ramp case, t h e a c f i e l d s b u i l d up uniformly during t h e f i r s t twelve cycles, the dc f i e l d during t h e second s e t of s i x cycles, from the seventh t o the t w e l f t h c y c l e o In a l l cases, the normalized amplitudes a r e less than f i v e times the i n i t i a l displacement. The r e s u l t s of these computations a r e summarized i n Figure 2. It is seen t h a t t h e magnitude of the "entrance t r a n s i e n t " given t h e ion s is g r e a t l y reduced through t h e use of the delayed dc ramp mode of operation,

EXPERlMENTAL

Apparatus The a d d i t i o n a l set of four e l e c t r o d e s a t the entrance of the quadrupole has been p r w i d e d i n the form of insula te d rod segments, one on each rod. The rod assemblies of the improved quadrupole, and the method used f o r energizing them a r e shown schematically i n Figure 3 , By muving the switch from position A t o B, t h e ope r a tion of the quadrupole is changed from conventional t o delayed dc ramp modes. The diameter of t h e rods is 0,6 inches, t h e i r length 10 inc he so The segments a r e 0.6 inches long, The e x c i t a t i o n frequency was 1.6 M H z .

Results Krypton g as was used f o r a l l obse r va tions made i n t h i s study. Resolving power measurements were made by observing t h e width of t h e mass 84 peak a t 10% h eig h t and the s e p a r a t i o n of t h i s peak from t h e mass 83 peak, Instrument s e n s i t i v i t i e s are p l o t t e d as f unc tions of r e s o l v i n g power a t d i f f e r e n t ion i n j e c t i o n e n e r g i e s and f o r ope r a tion i n t h e conventional and t h e delayed dc ramp modesa

The d a t a obtained a t 15-volt i o n i n j e c t i o n energy are presented i n Figure 4 , In t h i s in sta nc e the r e s o l v i n g power is l i m i t e d by t h e t r a n s i t t i m e of the ions, A t t h i s high i n j e c t i o n energy t h e ions traverse t h e f r i n g e ffelds i n less than t h r e e cycles, and t h e r e s u l t i n g transmission loss is n o m i n a l , m e n so, t h e s e n s i t i v i t y i n t h e delayed mode is s i x t i m e s t h a t of t h e conventional a t low r e s o l v i n g powers.
A t 8 ~ 0 l io n i n j e c t i o n energy t h e d i f f e r e n c e between t h e cont v e n t i o n a l and t h e delayed d c ramp modes of o p e r a t i o n is more apparent, a s shown i n Figure 5, The increased t i m e spent i n t h e quadrupole r a i s e s t h e r e s o l v i n g power v e r y appreciably. However, t h e g r e a t e r t i m e spent i n t h e f r i n g e f i e l d s of t h e conventional quadrupole causes a r a t h e r severe a t t e n u a t i o n of t h e transmission e f f i c i e n c y . A t a r e s o l v i n g power of 100 t h e instrument s e n s i t i v i t y of t h e delayed d c ramp mode i s 50 t i m e s t h a t of t h e conventional. A t a r e s o l v i n g power of 400, t h i s d i f f e r e n c e becomes a f a c t o r of 250!
Four-volt i n c i d e n t ions remain i n t h e system during a l a r g e number of cy cles of t h e a c voltage, and t h e nominal r e s o l v i n g power is high. However, i n t h e conventional quadrupole t h e s e n s i t i v i t y is t o o low t o be u s e f u l because the impulse given t h e ions i n t h e f r i n g e f i e l d s causes them t o strike the rods, and be l o s t . In t h e d c ramp mode, u s e f u l s e n s i t i v i t y i s achieved f o r r e s o l v i n g powers a s high as 650. These d a t a a r e shown i n Figure 6.

CONCLUSIONS

In t h e conventional quadrupole, a s h a s j u s t been shown, t h e use of low i n j e c t i o n energy inc r e a se s the number of c y c l e s spent by t h e ions i n t r a v e r s i n g t h e f r i n g e f i e l d s and causes se ve r e a t t e n u a t i o n of t h e tran smissio n e f f i c i e n c y . Conversely, i f high tr a nsmission e f f i c i e n c y is obtained by using highe r i o n i n j e c t i o n e ne r gie s, then t h e upper l i m i t of t h e resolving power is reduced, In t h e improved quadrupole, ope r a ting i n t h e delayed d c ramp mode, ions can be introduced a t luw e ne r gie s without causing t h e tr a nsmiss i o n e f f i c i e n c y t o be low. Thus high r e s o l v i n g power a t high s e n s i t i v i t y can be achieved.

A-10

REFERENCES

', W

Paul, H, P. Reinhard und U von Zahn, "Das Elektrische Massenfilter . als Massenspektrometer und Isotopentrenner," Zeitschrift fur Physik, Bd, 152, S, 143-182 (1958).

', M. Brubaker, "Auxiliary Electrodes of Quadrupole Mass Filters," W U, S, Patent 3,129,327, 3W, M. Brubaker, "The Quadrupole Mass Filter," Paper presented at IX Colloquium Spectroscopicurn Internationale, Juin, 1961, Lyon, France, "Study and Development of the Paul-type Mass Spectrometer," Contract No. AF 19(604)-5911, April, 1963.

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