8.

Preparation of a Positive Photoresist

Introduction
This experiment involves the preparation of a solution inhibitor, 1-diazo-1,2-
naphthoquinone-5-sulfonate and subsequent use of this molecule in a simple
positive photoresist. (expand this section a bit)
O O
O OH
O C
N2
h? H2O
+ N2

SO3 C8H1 7 SO3 C8H1 7 SO3 C8H1 7 SO3 C8H1 7

aqueous base insoluble aqueous base soluble

Background and Theory

Lithography is a technique used by the microelectronics industry in the
fabrication of integrated circuits. In this context, the lithographic process involves
using an exposure technique to transfer a pattern from a mask to a polymer film
and finally to a semiconducting substrate. A variety of modes of exposure can be
employed for this purpose including UV or X-ray radiation and electron- or ion-
beams. The photolithographic process,1,2 whose main features appear in Figure
1-1, employs UV radiation and is the primary technique currently used in
industrial applications. Briefly, a thin film (0.5 -10 ?m) of a photosensitive
polymer, termed a resist, which has been spin-coated onto a semiconducting
substrate is exposed to light through a mask. The mask is composed of a
pattern which prevents light from reaching certain regions of the resist and allows
it in other regions. Interaction of light with the resist induces a chemical change,
creating a latent image of the pattern from the mask, in the resist. This
photoinduced chemical change causes a difference in the dissolution rate
between exposed and unexposed regions. Development of the resist with an
appropriate solvent selectively dissolves the exposed or unexposed regions,
producing positive or negative tone images, respectively. After the development
step, regions of the substrate are left exposed, allowing them to be etched,
thereby transferring the pattern to the substrate. Finally, the remaining resist is
washed away to leave the bare, patterned substrate. Repetition of these steps
with different masks and resists allows for the construction of detailed 3-
dimensional circuit patterns.
 radiation
mask
photoresist
substrate

expose

latent image
develop

etch

strip

positive image negative image

The first positive resists were composed of a diazonaphthoquinone sensitizer as

the PAC and a copolymer of variously substituted phenols with aldehydes,
termed novolacs, as the polymer resin.1,5 In these positive resists, the exposed
regions of the film become more soluble to an aqueous base developper than the
unexposed regions. The solubility difference is derived from the fact that while
novolacs are soluble in aqueous base, diazonaphthoquinones are not, and their
presence in sufficient amounts inhibits solubilization of the resist prior to
exposure. However, the main photoproduct of the diazonaphthoquinone is base
soluble, thereby allowing solubilization of the resist after exposure to light. Upon
absorption of a photon, the diazonaphthoquinone loses nitrogen to form a
carbene which undergoes Wolff rearrangement to a ketene. The ketene is
attacked by water to form an indenecarboxylic acid.
Equipment and Chemicals
microscope slides, heavy-walled suction filtering flask, buchner funnel, filter
paper, opaque stencil/mask, 2-diazo-1-naphthol-5-sulfonic acid sodium salt
monohydrate, chlorosulfonic acid, 2-octanol, sodium bicarbonate, sodium
hydroxide, novolak resin, petroleum ether, acetone, water

Procedure
Preparation of 1-diazo-1,2-naphthoquinone-5-sulfonate
Caution-chlorosulfonic acid is corrosive and reacts violently with water
Note- the entire procedure must be performed in subdued light to avoid
premature initiation of the Wolff-rearrangement
1. Into a foil covered flask containing 3.0g of sodium 1-diazo-1,2-
naphthoquinone-5-sulfonate, carefully add chlorosulfonic acid (15 ml) so
as to maintain the reaction temperature below 60C.
2. Heat the reaction mixture with gentle stirring for 15 min at 65-70C. The
temperature should not be allowed to go above 75C in order to avoid
thermal activation of the Wolff rearrangement.
3. Cool the flask in an ice bath. Add chilled deionized water (100 ml)
dropwise down the thermometer such that the reaction temperature does
not exceed 75C. Caution-the addition of water to chlorosulfonic acid is
violently exothermic and liberates large quantities of gaseous HCl and
concentrated H2SO4.
4. Collect the solid yellow precipitate and carefully dispose of the filtrate.
5. To the solid add 2-octanol (15 ml) and aqueous Na2CO3 (10%, 20 ml).
6. Gently stir the reaction mixture at room temperature for 90 minutes.
7. Chill the reaction mixture in an ice bath until a yellow solid forms (several
minutes.
8. Collect the solid, wash it with cold water, air dry and wash with petroleum
ether.
9. Dissolve a small amount in deuterated chloroform and obtain an H NMR.
Then irradiate the solution in the NMR tube in the photoreactor until
subsequent NMR spectra show formation of the indene-carboxylic acid.

Preparation of the Photoresist

1. Dissolve the Novolak resin (0.5 g) in acetone (10 ml) with stirring.
2. Add 0.2 g of 1-diazo-1,2-naphthoquinone-5-sulfonate to the solution
and continue stirring until the mixture is homogeneous.
3. Being careful to protect the solution from light, dip a microscope slide
in a solution of the photoresist and allow it to dry in an oven at 60C for
30 minutes. It is important that all of the solvent be removed.
4. Place a mask (such as a key, coin, or photographic negative) over the
photoresist and irradiate each slide in the photoreactor equipped with
lamps in the ceiling for ? minutes.
5. Prepare 100 ml of developer solution: NaOH (?g) in 100 ml of water.
 6. Dip and gently swirl an exposed slide in the developer solution
adjusting the pH until dissolution times of about 4 minutes are
achieved.
7. Rinse the slide in dilute acid (pH<5) to remove xs base and stop
development reactions.
8. Repeat the exposure and development steps with other slides, varying
both exposure time and development time to improve image resolution.

Questions